Self‐Assembled Au/CdSe Nanocrystal Clusters for Plasmon‐Mediated Photocatalytic Hydrogen Evolution

Plasmon‐mediated photocatalytic systems generally suffer from poor efficiency due to weak absorption overlap and thus limited energy transfer between the plasmonic metal and the semiconductor. Herein, a near‐ideal plasmon‐mediated photocatalyst system is developed. Au/CdSe nanocrystal clusters (NCs) are successfully fabricated through a facile emulsion‐based self‐assembly approach, containing Au nanoparticles (NPs) of size 2.8, 4.6, 7.2, or 9.0 nm and CdSe quantum dots (QDs) of size ≈3.3 nm. Under visible‐light irradiation, the Au/CdSe NCs with 7.2 nm Au NPs afford very stable operation and a remarkable H₂‐evolution rate of (10× higher than bare CdSe NCs). Plasmon resonance energy transfer from the Au NPs to the CdSe QDs, which enhances charge‐carrier generation in the semiconductor and suppresses bulk recombination, is responsible for the outstanding photocatalytic performance. The approach used here to fabricate the Au/CdSe NCs is suitable for the construction of other plasmon‐mediated photocatalysts.     

Fast Photoelectric Conversion in the Near‐Infrared Enabled by Plasmon‐Induced Hot‐Electron Transfer

Interfacial charge transfer is a fundamental and crucial process in photoelectric conversion. If charge transfer is not fast enough, carrier harvesting can compromise with competitive relaxation pathways, e.g., cooling, trapping, and recombination. Some of these processes can strongly affect the speed and efficiency of photoelectric conversion. In this work, it is elaborated that plasmon‐induced hot‐electron transfer (HET) from tungsten suboxide to graphene is a sufficiently fast process to prevent carrier cooling and trapping processes. A fast near‐infrared detector empowered by HET is demonstrated, and the response time is three orders of magnitude faster than that based on common band‐edge electron transfer. Moreover, HET can overcome the spectral limit of the bandgap of tungsten suboxide (≈2.8 eV) to extent the photoresponse to the communication band of 1550 nm (≈0.8 eV). These results indicate that plasmon‐induced HET is a new strategy for implementation of efficient and high‐speed photoelectric devices.     

Facet‐Dependent Optical Properties Revealed through Investigation of Polyhedral Au–Cu2O and Bimetallic Core–Shell Nanocrystals

The ability to prepare Au–Cu₂O core–shell nanocrystals with precise control over particle size and shape has led to the discovery of facet‐dependent optical properties in cuprous oxide crystals. The use of Au cores not only allows the successful formation of Au–Cu₂O core–shell nanocrystals with tunable sizes, but also enables the observation of facet‐dependent optical properties in these crystals through the Au localized surface plasmon resonance (LSPR) absorption band. By tuning the Cu₂O shell morphology from rhombic dodecahedral to octahedral and cubic structures, and thus the exposed facets, the Au LSPR band position can be widely tuned. Such facet‐dependent optical effects are not observed in bimetallic Au–Ag and Au–Pd core–shell nanocrystals with the same precisely tuned particle sizes and shapes. It is believed that similar facet‐dependent optical properties could be observed in other ionic solids and other metal–metal oxide systems. The unusually large degree of plasmonic band tuning covering from the visible to the near‐infrared region in this type of nanostructure should be quite useful for a range of plasmonic applications.     

Plasmon‐Enhanced Spectroscopies with Shell‐Isolated Nanoparticles

Shell‐isolated nanoparticle‐enhanced Raman spectroscopy (SHINERS), due to its versatility, has been able to break the long‐term limitations of the material‐ and substrate‐specific generalities in the traditional field of surface‐enhanced Raman spectroscopy. With a shell‐isolated work principle, this method provides an opportunity to investigate successfully in surface, biological systems, energetic materials, and environmental sciences. Both the shell material and core morphology are being improved continuously to meet the requirements in diverse systems, such as the electrochemical studies at single crystal electrode surfaces, in situ monitoring of photoinduced reaction processes, practical applications in energy conversion and storage, inspections in food safety, and the surface‐enhanced fluorescence. Predictably, the concept of shell‐isolated nanoparticle‐enhancement could be expanded to the wider range for the performance of plasmon‐enhanced spectral modifications.     

Plasmonic Ag@Oxide Nanoprisms for Enhanced Performance of Organic Solar Cells

Localized surface plasmon resonance (LSPR), light scattering, and lowering the series resistance of noble metal nanoparticles (NPs) provide positive effect on the performance of photovoltaic device. However, the exciton recombination on the noble metal NPs accompanying above influences will deteriorate the performance of device. In this report, surface‐modified Ag@oxide (TiO₂ or SiO₂) nanoprisms with 1–2 nm shell thickness are developed. The thin film composed of P3HT/Ag@oxides and P3HT:PCBM/Ag@oxides is investigated by absorption, photoluminescence (PL), and transient absorption spectroscopy. The results show a significant absorption, PL enhancement, and long‐lived photogenerated polaron in the P3HT/Ag@TiO₂ film, indicating the increase of photogenerated exciton population by LSPR of Ag nanoprisms. In the case of P3HT/Ag nanoprisms, partial PL quench and relatively short‐lived photogenerated polaron are observed. That indicates that the oxides layer can effectively avoid the exciton recombination. When the Ag@oxide nanoprisms are introduced into the active layer of P3HT:PCBM photovoltaic devices, about 31% of power conversion efficiency enhancement is obtained relative to the reference cell. All these results indicate that Ag@oxides can enhance the performance of the cell, at the same time the ultrathin oxide shell prevents from the exciton recombination.     

Nanoconfined Nickel@Carbon Core–Shell Cocatalyst Promoting Highly Efficient Visible‐Light Photocatalytic H2 Production

The realization of large‐scale solar hydrogen (H₂) production relies on the development of high‐performance and low‐cost photocatalysts driven by sunlight. Recently, cocatalysts have demonstrated immense potential in enhancing the activity and stability of photocatalysts. Hence, the rational design of highly active and inexpensive cocatalysts is of great significance. Here, a facile method is reported to synthesize Ni@C core–shell nanoparticles as a highly active cocatalyst. After merging Ni@C cocatalyst with CdS nanorod (NR), a tremendously enhanced visible‐light photocatalytic H₂‐production performance of 76.1 mmol g^?1 h^?1 is achieved, accompanied with an outstanding quantum efficiency of 31.2% at 420 nm. The state‐of‐art characterizations (e.g., synchrotron‐based X‐ray absorption near edge structure) and theoretical calculations strongly support the presence of pronounced nanoconfinement effect in Ni@C core–shell nanoparticles, which leads to controlled Ni core size, intimate interfacial contact and rapid charge transfer, optimized electronic structure, and protection against chemical corrosion. Hence, the combination of nanoconfined Ni@C with CdS nanorod leads to significantly improved photocatalytic activity and stability. This work not only for the first time demonstrates the great potential of using highly active and inexpensive Ni@C core–shell structure to replace expensive Pt in photocatalysis but also opens new avenues for synthesizing cocatalyst/photocatalyst hybridized systems with excellent performance by introducing nanoconfinement effect.