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Constructing a hierarchical heterogeneous composite is deemed as an effective way to solve the current problems of metal oxides as lithium ion batteries’ anodes. In this work, we simultaneously designed the heterogeneous component and structure of the novel hybrid based on Kirkendall effect. The composite was composed of quasi-hexagonal Cu 1.5 Mn 1.5 O 4 nanoplates as a shell and CuO with voids as a core. The hybrids were characterized by using XRD, FTIR, TEM and SEM. It was found that the heating rate greatly influences the combination form of Cu 1.5 Mn 1.5 O 4 and CuO. The quasi-hexagonal Cu 1.5 Mn 1.5 O 4 nanoplates were assembled into branch-like shell decorated on the CuO surface under the low heating rate. However, the high heating rate led to a compact Cu 1.5 Mn 1.5 O 4 shell, although the shell was also assembled by quasi-hexagonal nanoplates. The reasonable formation mechanism of the unique component and structure was proposed. Such a hybrid with the branch-like shell exhibited the best lithium storage performance. The improved electrochemical performance can be attributed to the unique component and structure. Typically, the inside voids can alleviate the volume change and the hierarchical shell can provide much contact and reaction sites. This work not only opens a new view in constructing heterogeneous hybrid with unique structure by Kirkendall effect, but also can be expanded for many other structure-based applications, such as energy storage, sensors, and heterogeneous catalysts. [ABSTRACT FROM AUTHOR]

A dual-doping strategy was applied to fabricate the novel electrode materials. For the first time, the spinel hybrids of nanosized Ni x Co 1−x Fe 2 O 4 with N-doped graphene (N x -NG) were synthesized by a hydrothermal co-precipitation method. The size of Ni x Co 1−x Fe 2 O 4 (N x) nanoparticles on N-doped graphene can be tuned with the regulation of Ni/Co content. Among these nanocomposites, the Ni 0.4 Co 0.6 Fe 2 O 4 nanoparticles with the smallest average size of 10 nm are uniformly anchored on the N-doped graphene. The electrochemical characterizations display that the N 0.4 -NG exhibits the best electrochemical lithium storage performance compared to other five nanocomposites. It delivers a high capacity of 1367.0 mA h g−1 at the first discharge process，and the reversible capacity retention of 87% (2nd to 50th) at 0.1 A g−1. The excellent electrochemical performance of N 0.4 -NG can be owing to the small size of nanoparticles and its well-combination with N-doped graphene, which provide the large surface area and promote the ion/electron transfer rate. The synergistic effect resulted from the strong interaction between N 0.4 and N-doped graphene is contributed to the enhanced electrochemical performance of N 0.4 -NG. This study not only extends graphene-based electrode materials for lithium ion battery, but also promotes the development of energy resources. Unlabelled Image • A spinel hybrid of nanosized Ni x Co 1-x Fe 2 O 4 with N-doped graphene was fabricated. • Size of Ni x Co 1−x Fe 2 O 4 nanoparticles was tuned with the regulation of Ni/Co content. • A reversible capacity of 785.2 mA h g−1 of N 0.4 -NG after 50 cycles was obtained. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Mn doped Co 3 O 4 (Mn x Co y O) deposited on NF presents mesoporous nanoneedle structure. • Mn 1.5 Co 0.75 O/NF shows remarkable capacitance retention of 104% after 10,000 cycles. • The assembled ASC shows high energy density of 10.63 Wh kg−1 (at 14.7 kW kg−1). Abstract Long–term cycling stability is an important criterion and big challenge for pseudocapacitive materials. Ultra-stable manganese doped Co 3 O 4 mesoporous nanoneedles were synthesized via one-step hydrothermal reaction followed by annealing grown on nickel foam (noted as Mn x Co y O/NF, x + y = 2.25) for supercapacitors. The Mn doping in Co 3 O 4 was confirmed by several techniques. Among various Mn x Co y O/NF electrodes, the Mn 1.5 Co 0.75 O/NF demonstrated the superior electrochemical performance, with an excellent cycling stability of 104% capacitance retention after 10 000 charge–discharge cycles at 6 A g−1, as well as a good capability (668.4 F g−1 at 1 A g−1 compared to that of undoped Co 3 O 4 which is 201.3 F g−1). Moreover, the assembled asymmetric supercapacitor based on Mn 1.5 Co 0.75 O/NF//graphene performs a high energy density of 25.88 Wh kg−1 (at 359.5 W kg−1) and a high power density of 14.7 kW kg−1(at 10.63 Wh kg−1). The improved electrochemical properties are mainly owing to the enhanced intrinsic conductivity and electrochemical activity of Co 3 O 4 after doped with appropriate Mn concentration. The three-dimensional nanostructure of mesoporous nanoneedle array grown on NF also provides short ion diffusion path and large active surface areas, contributing to the high rate performance and high energy density. This study may offer a new approach to fabricate the unique 3D nanostructured electrode materials based on doped metal oxides for supercapacitors with long-term cycling stability and high energy density. [ABSTRACT FROM AUTHOR]

A self-template method is developed for hierarchically yolk-shelled NiCo 2 O 4 spheres (YS-NiCo 2 O 4 ) through a controlled hydrolysis process and followed by a thermal annealing treatment. The yolk-shelled NiCo 2 O 4 spheres possess out-shell consisting of hundreds of ultrathin sheets with 3–5 nm in thickness and solid yolk composing of a large number of nanoparticles. The YS-NiCo 2 O 4 generates a large specific surface area of 169.6 m 2 g −1 . Benefit from the large specific surface area and rich oxygen vacancy, the as-fabricated YS-NiCo 2 O 4 as electrode materials for supercapacitor exhibits high specific capacitance of 835.7 F g −1 at 0.5 A g −1 , an enhanced rate capability and excellent electrochemical stability with 93% retention after 10,000 cycles even at 10 A g −1 . Moreover, a hybrid supercapacitor combined with YS-NiCo 2 O 4 and graphene shows a high energy density of 34.7 Wh kg −1 at the power density of 395.0 W kg −1 at 0.5 A g −1 , even at 20 A g −1 , the hybrid supercapacitor still delivers the energy density of about 12.1 Wh kg −1 and the power density of 11697 W kg −1 . The desirable performance of yolk-shelled NiCo 2 O 4 suggests it to be a promising material as supercapacitor electrodes. [ABSTRACT FROM AUTHOR]

[Display omitted] • Three-dimensionally ordered mesoporous NiCo 2 O x @CeO y was developed by a hard template method. • Ce-doping can effectively adjust the electronic structure and bonding configuration of NiCo 2 O x electrode material. • The hollow cubic structure has high permeability and excellent bearing capacity. • The designed architecture has high specific surface area and abundant paths for electron/ion transport. • The NiCo 2 O x @CeO y //AC exhibits superior activity and stability for asymmetric supercapacitors. From the perspective of nano science and nanotechnology, it is very interesting and important to develop a reasonable and practical synthesis route of nanomaterials for production and life. Here, we develop a strategy of hollow cubic metal oxide nanocages. The method was inspired by Pearson's Hard-Soft-Acid-Base (HSAB) theory, and nanocages with excellent performance were prepared by coordination etching and optimization of reaction conditions. Firstly, Cu 2 O nanocubes were prepared by redox reaction at room temperature. Then, the hollow cubic NiCo 2 O x /CeO y nanocages were obtained by HSAB theory and cerium doping. The nanomaterial has a specific capacitance of up to 1976 F/g at the current density of 1 A/g. In addition, the asymmetric supercapacitor (ASC) prepared with hollow cubic NiCo 2 O x /CeO y nanocage as cathode and active carbon as anode exhibits an energy density as high as 37.1 Wh kg−1 at the power density of 375 W kg−1. The capacitance retention rate of the device is 91.5 % after 10,000 cycles. The device can be charged to light up LED lights. These excellent electrochemical properties, due to their unique structure and synergistic effect between materials, indicate the potential application value of hollow cubic NiCo 2 O x /CeO y nanocages in high-performance supercapacitors. [ABSTRACT FROM AUTHOR]

Ultrafine CuS nanoparticles anchored on nitrogen-sulfur co-doped graphene nanosheets are synthesized by a simple-green solvothermal method, the composite has excellent electrochemical performance for CO 2 reduction. [Display omitted] • The CuS/N, S-rGO was synthesized via a facile and environmentally friendly method. • The co-doping of N and S on graphene can promote the activation and conversion of CO 2. • CuS/N, S-rGO exhibits outstanding formate selectivity for CO 2 RR. Electrochemical conversion of CO 2 into hydrocarbons can effectively alleviate the energy crisis and promote carbon cycle. Herein, we report that small-size CuS nanoparticles are confined in nitrogen and sulfur co-doped reduced graphene oxide (CuS/N,S-rGO) for electrochemically reducing CO 2 to formate. Specifically, the CuS/N,S-rGO electrode achieves maximum Faradaic efficiency of 82% for formate formation at −0.63 V versus the reversible hydrogen electrode (RHE). Moreover, this catalyst exhibits a stable performance during 20 h-electrolysis. Experiments demonstrate that the doping of nitrogen and sulfur can create an abundance of active sites on the graphene nanosheets to accelerate the CO 2 reduction reaction (CO 2 RR). The CuS/N,S-rGO electrode exhibits excellent performance for CO 2 RR is attributed to the synergistic effect between N,S-rGO and CuS, and graphene can improve stability of composite. This work provides an efficient electrocatalyst for CO 2 RR and offers a facile and environmental friendly approach to synthesize small-size Cu-based composites. [ABSTRACT FROM AUTHOR]

Porous NiCo 2 S 4 nanosheets derived from bimetallic MOFs directly grow on a conductive substrate as a binder-free electrode. The unique open-structure NiCo 2 S 4 with porosity facilitates the diffusion of electrolyte and possess abundant electroactive sites, which presents a high specific capacity and long-term cycling stability. An assembled hybrid capacitor exhibits the practical performance of high energy density and excellent cycling property. • The porous NiCo 2 S 4 nanosheet arrays derived from bimetallic Metal-organic frameworks derivatives are prepared. • The effect of NiCo 2 S 4 morphology on electrochemical performance and reaction mechanism are discussed. • A hybrid supercapacitor device exhibits high energy density and superior cycling stability. Recently, metal-organic frameworks (MOFs) derived materials in the form of bulk powders with attractive chemical and structural properties show broad application in electrochemical energy storage. Bimetallic materials-based MOFs usually show better electrochemical properties than that of monometallic derivatives, while achieving the bimetallic MOFs-derived materials on current collector as a binder-free electrode is still a challenge. Here we report a new approach to directly obtain a binder-free electrode of bimetallic MOFs-derived NiCo 2 S 4 nanosheet arrays on nickel foam (NF) substrate. The porous NiCo 2 S 4 nanosheet arrays providing fast electrolyte permeation and rich electrochemical active sites, show an excellent specific capacity of 1354.4 C g−1, high rate performance, and outstanding cycling stability of 82.6% retention after 10,000 cycles. A hybrid supercapacitor assembled with the as-obtained binder-free electrode as a cathode and active carbon as an anode, exhibits high energy density of 49.1 Wh kg−1 at a power density of 375 W kg−1 and superior cycling stability of 94.5% retention after 10,000 cycles. These results offer a novel and general approach to construct binder-free electrode materials with advanced performance for the portable and practical energy storage device. [ABSTRACT FROM AUTHOR]

Zero-dimensional PdIr nanoalloys self-assembed to porous nanosheets with the help of capping agent PDDA. The PdIr PNS shows excellent OER and HER catalitic activities. • A simple route was used to self-stabilize ultrathin 0D PdIr nanocrystals into freestanding 2D porous PdIr nanosheets (PdIr PNSs). • The PdIr PNSs possessed large surface area-to-volume ratio and high density of exposed atoms. • The PdIr PNSs delivered excellent catalytic activities and stabilities. It remains a grand challenge to transform zero-dimensional (0D) noble-metal building blocks into well-defined two-dimensional (2D) architectures, which normally lacking an intrinsic driving force for anisotropic permutation in 2D manner. Herein, we report the first example of using a simple but efficient hydrothermal route to synthesize and self-stabilize ultrathin 0D PdIr NCs (2.4 nm) into a new class of freestanding 2D porous PdIr nanosheets with lateral size up to 1.5 μm (PdIr PNSs). Distinguished from previously reported 2D noble-metal nanosheets, the resultant 2D PdIr PNSs with immense surface area-to-volume ratio and high density of exposed atoms largely retain the special natures of 0D PdIr building blocks and further optimize their catalytic activity and stability at 2D manner. Electrochemical studies show that 2D PdIr PNSs deliver both excellent hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) activities with an HER overpotential of 40 mV and an OER overpotential of 285 mV affording 10 mA cm−2, outperforming those of 0D PdIr building blocks. The present work highlights the importance of tuning 0D nanocrystals at 2D manner for enhancing their OER and HER performance. [ABSTRACT FROM AUTHOR]

• Hierarchical layered Fe 3 O 4 QDs@C/rGO array derived from MIL-100(Fe)/GO. • Graphene and mesoporous carbon act as conductive support for anchoring Fe 3 O 4 QDs. • Multi-porous channels increase interface contacts and facilitate ion transportation. • Synergetic effect in Fe 3 O 4 QDs@C/rGO array results in the enhanced LIB performance. Herein, a double-buffering strategy is presented to boost the lithium storage potential of Fe 3 O 4. Firstly, the skeleton of MIL-100 (Fe) MOF is grown on graphene oxide, as a self-assembled template via in-situ solvothermal approach, which transform into ultrafine, well-dispersed and mesoporous carbon coated Fe 3 O 4 QDs (4 nm) imbedded on reduced graphene oxide (Fe 3 O 4 QDs@C/rGO), by pyrolysis. Each component in such a well-designed porous hierarchical structure significantly contributes to the remarkable enhancement of lithium ion storage performance, leading to high reversible capability with excellent prolonged cyclic stability after 2000 cycles (505 mAh g−1 at 2.0 A g−1). Both, Graphene sheets and mesoporous carbon act as conductive support for anchoring uniform Fe 3 O 4 QDs with confined double buffering for cyclic volume flux. Multi-channels with uniform mesopores in the self-assembled array and 4 nm QDs of Fe 3 O 4 confined in conductive carbon shells were favorable to enhance the interfacial electron/ion transfer, leading to the excellent rate and cycling performance with released volume changes upon Li+ insertion/extraction. The present research work provides a promising outset design and synthesis strategies for metal oxide QDs based nanocomposites, which may also be extended to the other electrode material system. [ABSTRACT FROM AUTHOR]