Improving the knowledge of the relationship between structure and properties is fundamental in catalysis. Recently, researchers have developed a variety of well-controlled methods to synthesize atomically precise metal nanoclusters (NCs). NCs have shown high catalytic activity and unique selectivity in many catalytic reactions, which are related to their ultrasmall size, abundant unsaturated active sites, and unique electronic structure different from that of traditional nanoparticles (NPs). More importantly, because of their definite structure and monodispersity, they are used as model catalysts to reveal the correlation between catalyst performance and structure at the atomic scale. Therefore, this review aims to summarize the recent progress on NCs in catalysis and provide potential theoretical guidance for the rational design of high-performance catalysts. First a brief summary of the synthetic strategies and characterization methods of NCs is provided. Then the primary focus of this reviewthe model catalyst role of NCs in catalysisis illustrated from theoretical and experimental perspectives, particularly in electrocatalysis, photocatalysis, photoelectric conversion, and catalysis of organic reactions. Finally, the main challenges and opportunities are examined for a deep understanding of the key catalytic steps with the goal of expanding the catalytic application range of NCs.

We demonstrate enhanced light–matter interactions in graphene–Au nanoparticle hybrid films and the application for high-quality SERS detection.

Chemically-triggered drug delivery systems (DDSs) have been extensively studied as they do not require specialized equipment to deliver the drug and can deeply penetrate human tissue. However, their syntheses are complicated and they tend to be cytotoxic, which restricts their clinical utility. In this work, the self-regulated drug loading and release capabilities of peptide-protected gold nanoclusters (Pep-Au NCs) are investigated using vancomycin (Van) as the model drug. Gold nanoclusters (Au NCs) coated with a custom-designed pentapeptide are synthesized as drug delivery nanocarriers and loaded with Van - a spontaneous process reliant on the specific binding between Van and the custom-designed peptide. The Van-loaded Au NCs show comparable antimicrobial activity with Van on its own, and the number of Van released by the Pep-Au NCs is found to be proportional to the amount of bacteria present. The controlled nature of the Van release is very encouraging, and predominantly due to the stronger binding affinity of Van with bacteria than that with Au NCs. In addition, these fluorescent Au NCs could also be used to construct temperature sensors, which enable the in vitro and in vivo bioimaging.

The chemical sensing for the convenient detection of mercuric ion (II) (Hg(2+)) have been widely explored with the use of various sensing materials and techniques. It still remains a challenge to achieve ultrasensitive but simple, rapid, and inexpensive detection to metal ions. Here we report a surface-enhanced Raman scattering (SERS) chip for the femtomolar (fM) detection of Hg(2+) by employing silver-coated gold nanoparticles (Au@Ag NPs) together with an organic ligand. 4,4'-Dipyridyl (Dpy) can control the aggregation of Au@Ag NPs via its dual interacting sites to Ag nanoshells to generate strong Raman hot spots and SERS readouts. However, the presence of Hg(2+) can inhibit the aggregation of Au@Ag NPs by the coordination with Dpy, and as a result the SERS signals of Dpy are quenched. On the basis of these findings, a SERS chip has been fabricated by the assembly of Au@Ag NPs on a piece of silicon wafer and the further modification with Dpy. The exchange of Dpy from the chip into the aqueous Hg(2+) droplet results in the quenching of Raman signals of Dpy, responding to 10 fM Hg(2+) that is about 6 orders of magnitude lower than the limit defined by the U.S. Environmental Protection Agency in drinkable water. Each test using the SERS chip only needs a droplet of 20 μL sample and is accomplished within ∼4 min. The SERS chip has also been applied to the quantification of Hg(2+) in milk, juice, and lake water.

The glutathione (GSH) level in human serum is closely associated with several life-threatening diseases, and tracing the aberrant GSH level can monitor the subhealth conditions at an early stage for human health prognosis. Developing portable and direct read-out mini-devices is an inevitable trend for reliable point-of-care (POC) detection of GSH in real-time/on-site conditions. We herein report a portable smartphone-sensing platform, a ratiometric fluorescence sensor combined with the 3D-printed smartphone device for rapid, sensitive, quantitative, and on-the-spot determination of GSH in human serum. The powerful fluorescence "off−on" nanoprobe was constructed by mixing the blue carbon dots (CDs) and orange gold nanoclusters (AuNCs) with the assistance of copper ions. The quenched fluorescence can be quickly restored upon interacting with GSH, showing a distinct color variation from blue to purple to orange. Integrated with the paper strip printed by the probe ink, the smartphone platform installed with a Color Recognizer App could accomplish sensitive, reliable, and real-time/on-site detection of GSH in human serum, which shows great significance for early disease diagnosis. The constructed smartphone platform is expected to develop into portable home medical equipment to realize convenient and rapid preliminary monitoring and self-assessment of health.

The interactions between visible light and sub-nanometer gaps were investigated by sandwiching graphene between two layers of vertically stacked Au nanoparticles. The optical properties of such a hybrid film have been effectively tuned by embedding a monolayer graphene, enabling a suppressed transmission of ∼16% accompanied by a red-shift of the resonant wavelength. Finite element simulations have shown that the strong coupling between two layers of plasmonic Au nanoparticles leads to an electric field enhancement of up to 88 times in graphene defined vertical gaps, in contrast to that of 14 times in the horizontal gaps between Au nanoparticles formed in the fabrication process. In addition, the size of gaps and thus the field enhancement can be readily tuned by the number of graphene layers sandwiched between Au nanoparticles. When being used as surface-enhanced Raman scattering (SERS) substrates, the Au nanoparticle/graphene/Au nanoparticle structures have demonstrated high Raman enhancement factors of up to 1.6 × 10(8) for RhB and 2.5 × 10(8) for R6G, and a detection limit of as low as 0.1 nM for Sudan III and methylene blue molecules.

A new Au–Pd alloy nanocluster (NC) – Au2Pd6S4(PPh3)4(C6H4F2S)6 is synthesized. The NC is applied to enhance the electrocatalytic HER activity of MoS2 compared with a single Pd or Au component.

We detail a facile method for enhancing the Raman signals of as-grown graphene on Cu foils by depositing gold nanoislands (Au Nis) onto the surface of graphene. It is found that an enhancement of up to 49 fold in the graphene Raman signal has been achieved by depositing a 4 nm thick Au film. The enhancement is considered to be related to the coupling between graphene and the plasmon modes of Au Nis, as confirmed by the finite element simulations. The plasmonic effect of the Au/graphene/Cu hybrid platform leads to a strong absorption at the resonant wavelength whose position shifts from visible light (640 nm) to near-infrared (1085 nm) when the thickness of Au films is increased from 2 nm to 18 nm. Finally, we demonstrate that hybrid substrates are reliable surface-enhanced Raman scattering (SERS) systems, showing an enhancement factor of ∼10(6) for dye molecules Rhodamine B and Rhodamine 6G with uniform and stable response and a detection limit of as low as 0.1 nM for Sudan III and Sudan IV.