Atomically thin iridium nanosheets for oxygen evolution electrocatalysis.

2D nanostructures of noble metals hold great potential for developing efficient electrocatalysts due to their high atom efficiency associated with their large specific surface area and abundant active sites. Here, we introduce a one-pot solvothermal synthesis method that can enable the fabrication of freestanding atomically thin Ir nanosheets. The thermal decomposition of a complex of Ir and a long-chain amine, which could readily be formed with the assistance of a strong base, under CO flow conditions successfully yielded Ir nanosheets consisting of 2-4 atomic layers. The prepared Ir nanosheets showed prominent activity and stability toward oxygen evolution electrocatalysis in acidic conditions, which can be attributed to their ultrathin 2D structure.

Directing Energy Flow in Core-Shell Nanostructures for Efficient Plasmon-Enhanced Electrocatalysis.

Conjugating plasmonic metals with catalytically active materials with controlled configurations can harness their light energy harvesting ability in catalysis. Herein, we present a well-defined core-shell nanostructure composed of an octahedral Au nanocrystal core and a PdPt alloy shell as a bifunctional energy conversion platform for plasmon-enhanced electrocatalysis. The prepared Au@PdPt core-shell nanostructures exhibited significant enhancements in electrocatalytic activity for methanol oxidation and oxygen reduction reactions under visible-light irradiation. Our experimental and computational studies revealed that the electronic hybridization of Pd and Pt allows the alloy material to have a large imaginary dielectric function, which can efficiently induce the shell-biased distribution of plasmon energy upon illumination and, hence, its relaxation at the catalytically active region to promote electrocatalysis.

Monitoring hydrogen transport through graphene by in situ surface-enhanced Raman spectroscopy.

Exploring the atomic or molecular transport properties of two-dimensional materials is vital to understand their inherent functions and, thus, to expedite their use in various applications. Herein, a surface-enhanced Raman spectroscopy (SERS)-based in situ analytical tool for the sensitive and rapid monitoring of hydrogen transport through graphene is reported. In this method, a reducing agent, which can provide hydrogen species, and a Raman dye self-assembled on a SERS platform are separated by a graphene membrane, and the reduction of the Raman dye by hydrogen species transferred through graphene is monitored with SERS. For validating the efficacy of our method, the catalytic reduction of surface-bound 4-nitrothiophenol by sodium borohydride was chosen in this study. The experimental results distinctly demonstrate that the high sensitivity and rapid detection ability of SERS can allow the effective analysis of the hydrogen transport properties of graphene.

Exploiting Plasmonic Hot Spots in Au-Based Nanostructures for Sensing and Photocatalysis.

ConspectusLocalized surface plasmon resonance is a unique property appearing in certain metal nanostructures, which can generate hot carriers (electrons and holes) and bring about an intense electromagnetic field localized near the surface of nanostructures. Specific locations, such as the rough surfaces and gaps in nanostructures, where a strong electromagnetic field is formed are referred to as hot spots. Hot-spot-containing plasmonic nanostructures have shown great promise in molecular sensing and plasmon-induced catalytic applications by exploiting the unique optical properties of hot spots. In this Account, we will review our recent developments in the synthesis of Au nanostructures consisting of multiple hot spots and Au-based heteronanostructures combining secondary active metals or semiconductors with Au nanostructures as promising plasmonic platforms for hot-spot-induced sensing and photocatalysis. We first provide a brief introduction to Au nanocrystals and Au nanoparticle assemblies with multiple hot spots. High-index-faceted hexoctahedral Au nanocrystals having multiple high-curvature vertices and edges are beneficial for the generation of an intense and reproducible electromagnetic field, which can enhance the performance of surface-enhanced Raman scattering-based molecular sensing. In addition, the engineering of interparticle gaps in Au nanoparticle assemblies to have a controlled size and a certain number of gaps can lead to the enhancement of plasmonic properties due to the significant amplification of the electromagnetic field at interparticle gaps. We then discuss hot-spot-containing Au-based heteronanostructures prepared by growing secondary components on the aforementioned Au nanostructures. With a combination of merit from strong plasmon energy formed by hot spots and catalytically active secondary materials, Au-based heteronanostructures have emerged as an attractive and versatile catalyst platform for various photocatalytic reactions. Through the control of key factors governing the photocatalysis of Au-based heteronanostructures, such as the coupling manner, shell thickness of secondary materials, and intimacy of contact, the plasmon energy formation of heteronanostructures and its transfer to catalytically active materials can be optimized, leading to the promotion of photocatalysis, such as photocatalytic hydrogen evolution. The rational design of Au nanostructures and Au-based heteronanostructures with multiple hot spots not only could realize enhanced sensing and photocatalysis but also could enable the understanding of the geometry-performance relationship. It is envisioned that the developed strategies can offer new opportunities for the design of various high-efficiency catalytic platforms.

Core-Shell Nanoparticle Clusters Enable Synergistic Integration of Plasmonic and Catalytic Functions in a Single Platform.

Designing controlled hybrid nanoarchitectures between plasmonic and catalytic materials is of paramount importance to fully exploit each function of constituent materials. This study reports a new synthetic strategy for the realization of colloidal clusters of core-shell nanoparticles with plasmonic cores and catalytically active shells. The Au@M (M = Pd or Pt) nanoparticle clusters (NPCs) with a high density of sub-1 nm interparticle gaps are successfully prepared by the deposition of M shells onto thermally activated Au NPCs. NPCs with other metal, metal sulfide, and metal oxide shells can also be synthesized by using the present approach. The prepared Au@M NPCs show remarkably enhanced plasmonic performance compared to their Au@M nanoparticle counterparts due to the localization of a strong electromagnetic field at the interparticle gaps, while the inherent catalytic function of shells is intact. In situ real-time Raman spectroscopy and plasmon-enhanced electrocatalysis experiments demonstrate that the controlled assembly of core-shell nanoparticles is a very effective route for the synergistic integration of plasmonic and catalytic functions in a single platform.