In Situ Tetraalkylammonium Ligand Engineering of Organic-Inorganic Hybrid Perovskite Nanoparticles for Enhancing Long-Term Stability and Optical Tunability.

Organic-inorganic hybrid perovskite nanoparticles (OIHP NPs) have attracted scientific attention owing to their efficient photoluminescence with optical tunability, which is highly advantageous for optoelectronic applications. However, the limited long-term stability of OIHP NPs has significantly hindered their practical application. Despite several synthetic strategies and encapsulation methods to stabilize OIHP NPs, complicated multi-step procedures are often required. In this study, we introduce an in situ ligand engineering method for stabilizing and controlling the optical properties of OIHP NPs using tetraalkylammonium (TAA) halides with various molecular structures at different concentrations. Our one-pot ligand engineering substantially enhanced the stability of the OIHP NPs without post-synthetic processes. Moreover, in certain cases, approximately 90% of the initial photoluminescence (PL) intensity was preserved even after a month under ambient conditions (room temperature, 20-50% relative humidity). To determine the role of ligand engineering in stabilizing the OIHP NPs, the surface binding properties of the TAA ligands were thoroughly analyzed using Raman spectroscopy. Specifically, the permanent positive charge of the TAA cations and consequent effective electrostatic interactions with the surfaces of the OIHP NPs are pivotal for preserving the initial PL intensity. Our investigation is beneficial for developing OIHP nanomaterials with improved stability and controlled photoluminescence for various optoelectronic applications, such as light-emitting devices, photosensitizers, photodetectors, photocatalysis, and solar cells.

Interfacial interactions of SERS-active noble metal nanostructures with functional ligands for diagnostic analysis of protein cancer markers.

Noble metal nanostructures with designed hot spots have been widely investigated as surface-enhanced Raman spectroscopy (SERS)-active substrates, particularly for selective and sensitive detection of protein cancer markers. For specific target recognition and efficient signal amplification, SERS probe design requires a choice of SERS-active nanostructures as well as their controlled functionalization with Raman dyes and target recognition entities such as antibodies. However, the chemical conjugation of antibodies and Raman dyes to SERS substrates has rarely been discussed to date, despite their substantial roles in detection schemes. The interfacial interactions of metal nanostructures with functional ligands during conjugation are known to be strongly influenced by the various chemical and physical properties of the ligands, such as size, molecular weight, surface charge, 3-dimensional structures, and hydrophilicity/hydrophobicity. In this review, we discuss recent developments in the design of SERS probes over the last 4 years, focusing on their conjugation chemistry for functionalization. A strong preference for covalent bonding is observed with Raman dyes having simpler molecular structures, whereas more complicated ones are non-covalently adsorbed. Antibodies are both covalently and non-covalently bonded to nanostructures, depending on their activity in the SERS probes. Considering that ligand conjugation is highly important for chemical stability, biocompatibility, and functionality of SERS probes, this review is expected to expand the understanding of their interfacial design, leading to SERS as one of the most promising spectroscopic analytical tools for the early detection of protein cancer markers.

Aqueous synthesis of highly monodisperse sub-100 nm AgCl nanospheres/cubes and their plasmonic nanomesh replicas as visible-light photocatalysts and single SERS probes.

Despite the distinctive electrochemical and photocatalytic properties of nanostructured silver chloride (AgCl), the shape- and size-dependence of their properties have not been thoroughly investigated to date. The most substantial reason responsible for this incomplete study and the subsequent limited applications is the failure in controlling the structure of AgCl nanomaterials, mainly owing to the challenging synthetic conditions including organic phase and high reaction temperature. In this work, we reported a rapid one-pot room-temperature aqueous synthesis of highly monodisperse sub-100 nm AgCl nanomaterials with various shapes and sizes by controlling the precursor (Ag+ and AuCl4 -) ratios. The remaining unreacted metal precursors (Ag+ and AuCl4 -) used to produce AgClNC were subsequently reduced by ascorbic acid on the surface of the synthesized AgCl nanomaterials to form Ag/Au bimetallic nanomesh structures (AgClNC#AuAgCMs and SMs). After the removal of the AgCl nanotemplates, only nanomesh structures (AuAgCMs and SMs) were obtained. Importantly, we successfully decreased the size of the AgCl nanomaterials which were replicated into bimetallic spherical and cubic nanomesh structures that were small enough (∼100 nm) to show intense surface-plasmon-absorption bands. Based on these unique chemical and physical properties, we could take advantage of the plasmonic photocatalysis properties of the complex comprising semiconducting AgCl/metallic nanomesh replica for the complete removal of the environmentally harmful Cr6+ in the presence of sacrificial agents such as formic acid. Finally, the novel bimetallic nanomesh structures proved themselves to exhibit intense surface-enhanced Raman scattering properties in a single-particle enhancing the electromagnetic field.

Unveiling the Role of Precursors in the Byproduct Formation of AgCl-Replicated Bimetallic Nanostructures and Their Stability-Dependent Photothermal Properties.

AgCl nanomaterials recently attracted scientific interest as useful structural building blocks for producing metallic nanomaterials owing to their facile synthesis, controllable morphology, and ease of removal under ambient conditions. However, their complex chemical reactivity has primarily been studied in association with water solubility or reducibility. This study investigates the pivotal role of precursor ligands in the photochemical synthesis of metallic cubic mesh nanostructures on the AgCl templates. The side reactions between AgCl and Au precursors with different ligands are thoroughly discussed along with their influence on the byproduct formation and the structural stability of the resulting metallic nanostructures. Importantly, we introduce for the first time the partial destruction of AgCl and the formation of undesirable byproducts caused by the presence of highly oxidizing and Cl-containing AuCl4-. In addition, a synthetic route for producing highly pure and stable metallic nanostructures using a halogen-free Au precursor or Pt-priming is proposed. Further, the photothermal properties of these replicated metallic nanostructures are presented as a new evaluation tool for analyzing their overall structural stability. Discovering the role of precursor ligands in the reaction system will prove useful as a guide for the synthesis of functional noble metal nanomaterials using silver halide templates.

Wrapping AgCl Nanostructures with Trimetallic Nanomeshes for Plasmon-Enhanced Catalysis and in Situ SERS Monitoring of Chemical Reactions.

Selective chemical control of multiple reactions is incredibly important for the fabrication of sophisticated nanostructures for functional applications. A representative example is the synthesis of plasmonic nanomaterial-silver chloride (AgCl) conjugates, where metal ions should be selectively reduced into metallic nanostructures for plasmon-enhanced catalytic activity, while the reducible AgCl nanomaterials remain intact despite the presence of a chemical reductant. In addition to the selectively controlled reduction, the plasmonic nanostructures should be appropriately designed for the high stability and photoefficiency of catalysts. In this study, we demonstrate how AgCl nanocubes and nanospheres could be comprehensively wrapped by plasmonic three-dimensional nanomesh structures consisting of gold, silver, and palladium by the selective reduction of their ionic precursors while the AgCl nanostructures remain intact. Complete trimetallic wrapping provided the absorption of visible light, while the porosity of the nanomesh structures exposed the photocatalytic AgCl surface to catalyze desired reactions. Platinum in place of palladium was examined to demonstrate the versatility of the wrapping scheme, resulting in an extraordinary catalytic activity. Importantly, the detailed chemical mechanism behind the trimetallic wrapping of the AgCl nanostructures was systematically investigated to understand the roles of each reaction component in controlling the chemical selectivity. The synthesized AgCl-trimetal nanoconjugates excellently exhibit both metal-based and plasmon-enhanced catalytic properties for the removal of environmentally harmful Cr6+. Moreover, their applications as surface-enhanced Raman-scattering (SERS) probes for the in situ monitoring of catalytic reduction in real-time and as single-nanoparticle SERS probes for molecular detection are thoroughly demonstrated.