Single crystalline gold nanorods (Au NRs) dominated by {110} side facets were employed as seeds to tailor the deposition of Ag. Apart from homogeneous coating, anisotropic coating of Ag was observed and resulted in an orange slice-like shape for the Au@Ag nanocrystal. Different growth rates for the {110} side facets were responsible for this shape: among the four {110} facets, two of the neighboring {110} facets grew more quickly and another two grew more slowly, thus inducing the anisotropic deposition of Ag around the Au NR. This growth behavior is believed to be a consequence of competition between the strong stabilization of cetyltrimethylammomium bromide (CTAB) molecules to the {110} facets of Ag and minimization of the overall surface energy. Although the reason for the anisotropic coating remains to be clarified, our results lead to one important conclusion: The interaction of CTAB and metal can be utilized to tune the shapes of bimetallic structures.
In this letter, we report the competing growth of a Pd shell on the {110} and {100} facets of Au nanorods (Au NRs). This results in the disappearance of unstable {110} facets and the formation of rectangularly shaped Pd/Au bimetallic nanorods that show only four stable {100} side surfaces. The energy minimization to a more stable morphology is believed to be the driving force for the formation of the rectangular shape of the Pd shell.
Rational construction of atomic‐scale interfaces in multiphase nanocomposites is an intriguing and challenging approach to developing advanced catalysts for both oxygen reduction (ORR) and evolution reactions (OER). Herein, a hybrid of interpenetrating metallic Co and spinel Co3O4 “Janus” nanoparticles stitched in porous graphitized shells (Co/Co3O4@PGS) is synthesized via ionic exchange and redox between Co2+ and 2D metal–organic‐framework nanosheets. This strategy is proven to effectively establish highways for the transfer of electrons and reactants within the hybrid through interfacial engineering. Specifically, the phase interpenetration of mixed Co species and encapsulating porous graphitized shells provides an optimal charge/mass transport environment. Furthermore, the defect‐rich interfaces act as atomic‐traps to achieve exceptional adsorption capability for oxygen reactants. Finally, robust coupling between Co and N through intimate covalent bonds prohibits the detachment of nanoparticles. As a result, Co/Co3O4@PGS outperforms state‐of‐the‐art noble‐metal catalysts with a positive half‐wave potential of 0.89 V for ORR and a low potential of 1.58 V at 10 mA cm−2 for OER. In a practical demonstration, ultrastable cyclability with a record lifetime of over 800 h at 10 mA cm−2 is achieved by Zn–air batteries with Co/Co3O4@PGS within the rechargeable air electrode.
One‐dimensional structures of nitrogen‐rich carbon nitride are synthesized via a thermal evaporation process. The CN atomic rings (s‐triazine and/or tri‐s‐triazine) present in the precursor remain stable during the thermal evaporation and vapor transfer. They act as basic building blocks during the microstructure assembly; thus ensuring a high nitrogen content in the final product.
Single crystalline Au nanorods (Au NRs), synthesized via seed-mediated growth, show unique surface structures. Apart from the oft-observed {100} and {111} facets, unexpectedly, unstable {110} facets dominate in such nanorods due to {110} restricted growth. Unique properties have been suggested for the nanorods. One novel property, we believe, is that the the high-energy {110} endows the nanorod with a high reactivity, thus making the growth to more stable morphologies possible. Herein, by switching the growth to the {110} preference, we successfully obtained thermodynamically more stable morphologies (arrow-headed gold nanorods and gold nano-octahedra) with a high quality and yield. A blockade of selective underpotential deposition of silver is suggested to be responsible for the switching.
A simple and facile method was developed to fabricate alloyed Pt−Ag nanoislands on Au nanorods (denoted as Au@Pt−Ag NRs). The island growth mode of Pt on the Au rod was employed to guide the growth behavior of Pt−Ag alloys. The formation of the Pt−Ag alloy was confirmed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), XRD (X-ray diffraction), XPS (X-ray photoelectron spectroscopy), UV−visible absorption spectra, and electrochemical characterization. The alloy compositions can be tuned within the broad miscibility gap from Ag9Pt91 to Ag83Pt17 by controlling the ratios of PtCl4
2−/Ag+
. The Au@Pt−Ag NRs show tunable surface plasmon resonance (SPR) and enhanced catalytic activity for methanol electro-oxidation, pointing to a potential future of nanometerized Pt−Ag alloys in fuel cells and other related fields. Apart from Pt−Ag, this strategy may be applied to the formation of Pt-related bimetallic (trimetallic) systems.
A 3D porous sulfur/graphene@g‐C3N4 (S/GCN) hybrid sponge, which can be directly applied as a free‐standing cathode for Li–S batteries, is realized via a microemulsion assisted assembly approach. In this strategy, the interior oil emulsion droplets serve as soft templates to form pores to accommodate sulfur and the hydrophilic GCN stacks around oil droplets to assemble into a crosslinked 3D network. Through this microemulsion encapsulation route, S/GCN cathodes with a sulfur loading as high as 82 wt% can be achieved. Furthermore, the enriched N‐sites in GCN macropores offer numerous adhesion sites for polysulfides, realizing a “physical‐chemical” dual‐confinement for polysulfides from diffusion. Moreover, the robust and highly porous 3D graphene frameworks render efficient electron/Li+ transport pathways for fast kinetics as well as good structure integrity. Consequently, in comparison to the conventional G‐sponge/Li2Sn catholyte system, S/GCN delivers a higher specific capacity, superior high‐rate capability (612 mA h g−1 at 10 C), and alleviated anode corrosion issues. Particularly, an energy density as high as 1493 W h kg−1 (calculated on the total weight of the cathode) and an extremely low capacity fading rate of 0.017% per cycle over 800 cycles at 0.3 C are achieved.
2D hierarchically porous carbon (2D-HPC) nanosheets with unique advantages are highly desired as host materials for lithium sulfur (Li-S) batteries and other energy storage devices. Herein, we propose a self-template and organic solvent-free approach to synthesize nanosheets of monoclinic ZIF-8 at room temperature from which 2D-HPC nanosheets (ZIF-8 nanosheets carbon denoted as ZIF-8-NS-C) are derived to be an efficient sulfur immobilizer for Li-S batteries for the first time. The anisotropic nanosheets are believed to relate to the symmetry of the monoclinic structure. The 2D ZIF-8-NS-C nanosheets with embedded hierarchical pores construct an effective conductive network through "plane-to-plane" modes to endow superior electron transfer and fast electrochemical kinetics. Moreover, the nitrogen-rich feature of ZIF-8-NS-C can increase the affinity/interaction of carbon host with lithium polysulfides, favoring the cyclic performance. The sulfur/ZIF-8-NS-C (S/ZIF-8-NS-C) cathode shows a superior rate capability with high capacities of 1226 mA h g at 0.2 C and 785 mA h g at 2 C, and a sustainable cycling stability with a capacity attenuation of 0.12% per cycle at 0.5 C for 300 cycles. The approach proposed here pioneers the controllable design of MOF-based structures to inspire the exploration of more variable MOF-derived porous materials for energy storage applications.
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