The electrical, optical and other important properties of colloidal nanocrystals are determined mainly by the crystals' chemical composition, size and shape. The introduction of specific dopants is a general approach of modifying the properties of such nanocrystals in well-controlled ways. Here we show that in addition to altering the atomic composition of the nanocrystals the introduction of specific dopants can also lead to dramatic changes in morphology. The creation of Mg-doped ZnO nanocrystals provides an excellent example of this procedure; depending on the molar ratio of dopant precursor in the reagents, doped nanocrystals with well-defined shapes, from tetrapods to ultrathin nanowires, which exhibit tunable optoelectronic properties, are obtained for the first time. We find that the Mg dopants play an important role in the primary growth stage, resulting in initial growth seeds having diverse crystallographic structures, which are critical for the generation of doped nanocrystals with different shapes. We demonstrate that this "greener" synthetic scheme can be extended to other dopant systems and provides an attractive and effective strategy for fabricating doped ZnO nanocrystals with interesting compositional and spatial complexity.

Metal–organic frameworks (MOFs) have been considered as a class of promising electrode materials for supercapacitors owing to their large surface area, rich porosity, and variable redox sites; however, direct application of pristine MOFs in energy storage has been largely hindered by their poor electrical conductivity and stability issues. In this work, we demonstrate a facile two-step approach to address the controlled growth of Ni-MOF arrays on the surface of NiCo2O4 nanowires by modulating the formation reaction of MOFs. By taking advantage of the intriguing merits from the NiCo2O4 core and Ni-MOF shell as well as their synergistic effects, the optimized NiCo2O4@Ni-MOF hybrid electrode exhibits boosted electrochemical performance, in terms of high specific capacity (208.8 mA h/g at 2 mA/cm2) and good rate capability. In addition, the assembled flexible solid-state HSC device based on the optimized NiCo2O4@Ni-MOF and activated carbon as the cathode and anode achieves a maximum energy density of 32.6 W h/kg at a power density of 348.9 W/kg without sacrificing its outstanding cycling performance (nearly 100% retention over 6000 cycles at 8 mA/cm2) and mechanical stability, outperforming most recently reported MOF-based HSC devices in an aqueous electrolyte. Our work demonstrates the possibility of exploiting novel MOF-based hybrid arrays as battery-type electrodes with enhanced electrochemical properties, which exhibits great potential in flexible energy storage devices.

Hierarchical NiCo2O4@NiMoO4 core–shell nanowire/nanosheet arrays were successfully fabricated and assembled in an asymmetric supercapacitor device with outstanding electrochemical performance.