RESUMEN
The design of efficient electrocatalysts for improving hydrogen evolution reaction (HER) performance using atomically precise metal nanoclusters (NCs) is an emerging area of research. Here, we have studied the HER electrocatalytic performance of monometallic Cu6 and Au6 nanoclusters and bimetallic Au4Cu2 nanoclusters. A bimetallic Au4Cu2/MoS2 composite exhibits excellent HER catalytic activity with an overpotential (η10) of 155 mV vs. reversible hydrogen electrode observed at 10 mA cm-2 current density. The improved HER performance in Au4Cu2 is due to the increased electrochemically active surface area (ECSA), and Au4Cu2 NCs exhibits better stability than Cu6 and Au6 systems and bare MoS2. This augmentation offers a greater number of active sites for the favorable adsorption of reaction intermediates. Furthermore, by employing X-ray photoelectron spectroscopy (XPS) and Raman analysis, the kinetics of HER in the Au4Cu2/MoS2 composite were elucidated, attributing the favorable performance to better electronic interactions occurring at the interface between Au4Cu2 NCs and the MoS2 substrate. Theoretical analysis reveals that the inherent catalytic enhancement in Au4Cu2/MoS2 is due to favorable H atom adsorption over it and the smallest ΔGH* value. The downshift in the d-band of the Au4Cu2/MoS2 composite influences the binding energy of intermediate catalytic species. This new catalyst sheds light on the structure-property relationship for improving electrocatalytic performance at the atomic level.
RESUMEN
Single-molecule spectroscopy (SMS) is a unique and competent technique to study molecule dynamics and sense biomolecules precisely. The design of an ultrahigh-stability single fluorophore probe with excellent photostability and long-lived dark transient states for single-molecule fluorescence microscopy is challenging. Here, we found that the photostability of bimetallic AuAg28 nanoclusters is better than monometallic Ag29 nanoclusters. The photon antibunching experiments unveiled exceptional brightness and remarkable photostability with high survival times of up to 218 s with minimal blinking. AuAg28 NCs exhibited longer "on" times and shorter "off" times as compared to Ag29 NCs. The statistical analysis was performed on at least 100 molecules that showed single-step photobleaching and almost a 5-fold enhancement in intensity on Au doping in Ag29 NCs. The distinctive and tunable photophysics of metal NCs can offer huge potential in pushing single-molecule dynamic measurements to be carried out biologically.
RESUMEN
Bimetallic nanoclusters (NCs) have emerged as a new class of luminescent materials for potential applications in sensing, bio-imaging, and light-emitting diodes (LEDs). Here, we have synthesized gold-copper bimetallic nanoclusters (AuCu NCs) using a one-step co-reduction method and tuned the emission wavelength from 520 nm to 620 nm by changing the [Cu2+]/[Au3+] molar ratio. The quantum yield (QY) increases from 6% to 13% upon incorporation of the Cu atom in the Au NCs. MALDI-TOF mass spectrometric analysis reveals that the composition of the Au NCs is Au6(MPA)5, and the bimetallic nanocluster is Au4Cu2(MPA)5, where 3-mercaptopropionic acid (MPA) is used as the capping ligand. Furthermore, we investigated the optimized structures of the as-synthesized NCs using density functional theory (DFT) along with analysis of the preferable adsorption sites using Fukui functions. We report the HOMO-LUMO gap, which is consistent with the experimentally observed red shift in the UV-Vis absorption features of the Au NCs upon copper doping. XPS studies suggest the formation of intermixing of states between the 5d orbitals of Au and the 3d orbitals of Cu in the AuCu NCs after incorporating Cu atoms into the Au NCs, which is corroborated by the DFT calculations on electronic charge transfer from the Cu to the Au atom in the NCs. The coupling between Au(I) and Cu(I) facilitates the formation of a low-lying mixed Au(I)-Cu(I) energy state. This study elaborates on the impact of Cu doping on the excited-state relaxation dynamics of AuCu NCs.
RESUMEN
Studies on self-assembly of metal nanoclusters (MNCs) are an emerging field of research owing to their significant optical properties and potential applications in many areas. Fabricating the desired self-assembly structure for specific implementation has always been challenging in nanotechnology. The building blocks organize themselves into a hierarchical structure with a high order of directional control in the self-assembly process. An overview of the recent achievements in the self-assembly chemistry of MNCs is summarized in this review article. Here, we investigate the underlying mechanism for the self-assembly structures, and analysis reveals that van der Waals forces, electrostatic interaction, metallophilic interaction, and amphiphilicity are the crucial parameters. In addition, we discuss the principles of template-mediated interaction and the effect of external stimuli on assembly formation in detail. We also focus on the structural correlation of the assemblies with their photophysical properties. A deep perception of the self-assembly mechanism and the degree of interactions on the excited state dynamics is provided for the future synthesis of customizable MNCs with promising applications.