Advanced hybrid nanomaterials tailored with unique morphologies and multiple functions can be synthesized by the controllable integration of two or more well‐designed components. Distinctively shaped metal cores with well‐defined coordination polymer shells can lead to synergistic structural properties in the resultant hybrid materials. Herein, we report a facile synthetic strategy for gold multipod nanoparticle (GMN) cores‐zeolitic imidazolate framework (ZIF‐67) shells (GMN@ZIF‐67) nanohybrids. Because of the structural anisotropy, which is crucial for heterogeneous seed‐induced nucleation, and uniqueness of GMNs, their combination with ZIF‐67 gives characteristic core–shell materials. The synthetic process can be readily achieved without using surfactants or capping reagents. Thus, it is potentially an environmentally friendly route to expedient nanohybrids. The material properties (i.e., surface area, size, and shape) of the resultant GMN@ZIF‐67 nanohybrids can be readily controlled by simply varying the relative amount of GMNs and ZIF‐67 precursors used.
Inorganic
hybrid materials with anisotropic noble-metal nanoparticle cores and
cagelike transition-metal chalcogenide shells are promising candidates
for a wide variety of applications. Herein, we report an effective
fabrication method for gold multipod nanoparticle (GMN) core–cobalt
sulfide shell (GMN@Co
x
S
y
) nanostructures. The unique cagelike morphology is successfully
acquired within nanohybrids (GMN@Co
x
S
y
nanocages). The cobalt-based metal–organic
frameworks can act as versatile sacrificial templates to the desired
hybrid nanomaterials through solution-based etching approaches without
any undesirable reshaping of GMNs, which are embedded within. Examination
of the electrocatalytic oxygen evolution reaction (OER) of the prepared
nanohybrids reveals that a type of GMN@Co
x
S
y
nanohybrid shows a substantially lower
overpotential (η) value (345 mV) compared with those of GMNs
(617 mV) and Co
x
S
y
nanomaterials (418 mV) at a current density of 10 mA cm–2. The enhanced OER performance is mainly attributed
to the highly effective core–shell interfaces stemming from
the unique multibranch topologies of the GMN cores as well as the
optimized cobalt sulfide shells of the nanohybrids.
Effective incorporation of multiple types of ligands in a given coordination structure provides structural complexity and functional diversity to the resultant coordination‐driven assembly. One of the most widely used synthetic approaches is the utilization of the molecular symmetry principle to combine multiple ligands and specific metallic centers in a preferred manner. The variation of metal ions can be helpful to understand the importance of symmetry for the generation of structurally hierarchical supramolecular platforms. We describe the synthesis and characterization of isostructural supramolecular helicates, [M8(PDA)6(AIP)3(DMF)6−x(H2O)x] (M=Ni (1), Co (2), and Mn (3); PDA=2,6‐pyridinedicarboxylate; AIP=5‐aminoisophthalate; x=0 for 1, and x=4 for 2 and 3). The effect of metal variation on the formation of supramolecular helicates and their solid‐state crystal packing are discussed. Despite the disparity in the ionic radii and distinct coordination‐geometry preferences of Co2+, Ni2+, and Mn2+, all metal centers engaged in the assembly with the heteroleptic ligands in the same manner to form isostructural supramolecular helicates.
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