Epitaxial growth is one of the most commonly used strategies to precisely tailor heterostructures with well-defined compositions, morphologies, crystal phases, and interfaces for various applications. However, as epitaxial growth requires a small interfacial lattice mismatch between the components, it remains a challenge for the epitaxial synthesis of heterostructures constructed by materials with large lattice mismatch and/or different chemical bonding, especially the noble metal-semiconductor heterostructures. Here, we develop a noble metal-seeded epitaxial growth strategy to prepare highly symmetrical noble metal-semiconductor branched heterostructures with desired spatial configurations, i.e., twenty CdS (or CdSe) nanorods epitaxially grown on twenty exposed (111) facets of Ag icosahedral nanocrystal, albeit a large lattice mismatch (more than 40%). Importantly, a high quantum yield (QY) of plasmon-induced hot-electron transferred from Ag to CdS was observed in epitaxial Ag-CdS icosapods (18.1%). This work demonstrates that epitaxial growth can be achieved in heterostructures composed of materials with large lattice mismatches. The constructed epitaxial noble metal-semiconductor interfaces could be an ideal platform for investigating the role of interfaces in various physicochemical processes.

One‐dimensional (1D) hyperbranched heterostructures (HBHSs) with abundant interfaces are rendered with various interfacial phenomena and functionalities. However, the rational synthesis of 1D HBHSs with desired spatial architecture and specific interface remains a great challenge. Here, we report a seeded growth method for controlled synthesis of two extraordinary types of HBHSs, in which high‐intensity of CdS branches selectively grow on 1D nanowire (NW) trunks with different growth behaviors. The composition of the HBHSs can be further tuned by combining with cation exchange method, which enriches the variety of the HBHSs. The optoelectronic devices based on a single HBHS were fabricated and exhibit a better photoresponse performance compared with that of a single NW trunk. This advance provides a strategy for the controlled synthesis HBHSs with complex morphology and offers a platform for exploring their applications for photo harvesting and conversion.

1D/2D heterostructures, in particular those that consist of a 1D nanorod core and a 2D nanoplate (NPL) shell, enable the combination of the merits and mitigation of the demerits of distinct dimensionalities into one system, providing a new platform to study their intriguing properties. However, there is still lack of effective strategies to rationally integrate the components with different dimensionalities together. Here, we report a general seeded growth method for the construction of epitaxial 1D/2D heterostructures with a variety of compositional combinations, in which ordered 2D NPL arrays are vertically grown along the c-axis of 1D wurtzite nanomaterials, including II− VI and I−III−VI 2 semiconductors. The loading densities of NPLs on the 1D nanomaterials are very high, up to 280 piece/μm. The same crystal structure of the grown NPLs and 1D seeds ensures the epitaxial growth relationship between these two materials. It is found that the secondary 2D growth mode is a kinetic-dominated process, in addition to the effect of the anionic sulfur precursor. The as-prepared 1D/2D CdSe/CdS heterostructures exhibit enhanced activity for photocatalytic hydrogen evolution compared to that of the single-component CdSe NRs and CdS/CdS homostructures. This work greatly enriches the variety and architecture of the available heterostructures and also provides a toolbox for exploring their promising applications.

Ternary metal sulfide emerged as an important semiconductor for optoelectronic and photocatalytic applications. However, controlled synthesis of ultrathin ternary metal sulfide nanoplates is still difficult due to the lack of strategies to fulfill the anisotropic growth. Here, we report a wet-chemistry method for the preparation of ultrathin indium-based ternary metal sulfide (MIn 2 S 4 , M = Zn, Cd, and Ni) nanoplates with thickness within 2 nm, in which the as-grown β-In 2 S 3 nanoplates are used as templates. As a proof of concept, the photocatalytic hydrogen evolution of ZnIn 2 S 4 nanoplates is performed, which shows a remarkable photocatalytic performance under the irradiation of simulated sunlight. After loading of Ni nanoparticles as cocatalysts, it is found that the 3.0 wt % Ni/ZnIn 2 S 4 photocatalysts exhibit the best performance for hydrogen generation with a rate of 19.9 mmol•g −1 •h −1 , which is 6 times larger than that of ZnIn 2 S 4 nanoplates. The present work provides a method for the development of high-quality ultrathin multinary sulfide nanoplates.

One‐dimensional (1D) hyperbranched heterostructures (HBHSs) with abundant interfaces are rendered with various interfacial phenomena and functionalities. However, the rational synthesis of 1D HBHSs with desired spatial architecture and specific interface remains a great challenge. Here, we report a seeded growth method for controlled synthesis of two extraordinary types of HBHSs, in which high‐intensity of CdS branches selectively grow on 1D nanowire (NW) trunks with different growth behaviors. The composition of the HBHSs can be further tuned by combining with cation exchange method, which enriches the variety of the HBHSs. The optoelectronic devices based on a single HBHS were fabricated and exhibit a better photoresponse performance compared with that of a single NW trunk. This advance provides a strategy for the controlled synthesis HBHSs with complex morphology and offers a platform for exploring their applications for photo harvesting and conversion.