Ag Nanoprisms Research Articles

Silver nanoprism-mediated colourimetric sensing probe for efficient detection of Pd(II) and Pt(II) ions in water and reuse of formed bimetallic nanoprisms

Sensitive and selective methods for detecting Pd(II) and Pt(II) ions in water are crucial for environmental monitoring and remediation. Although traditional methods for detection of Pd(II) and Pt(II) ions are accurate and sensitive, they face substantial challenges due to high costs, reliance on specialised equipment and limited field applicability, thereby presenting notable limitations. In this study, we introduce a novel colourimetric sensing probe designed specifically to identify Pd(II) and Pt(II) ions in aqueous solutions. This probe utilises the enhanced chemical stability of Ag nanoprisms achieved through Pd or Pt deposition on their surfaces. Our approach features exceptionally low limits of detection of 2.6 nM for Pd(II) and 0.3 nM for Pt(II), indicating an impressive detection range. Furthermore, the probe’s ease of use, cost-effectiveness and compatibility with both naked eye and UV–Vis spectrophotometric detection make it a selective, reliable and affordable option for point-of-care analysis. Beyond its impressive sensitivity for ion detection, this methodology offers the additional benefit of enabling the on-demand synthesis of customised bimetallic catalysts. The synthesised Ag/Pd and Ag/Pt bimetallic nanoprisms demonstrate promising catalytic potential for environmental remediation. This advancement paves the way for efficient recycling and reuse of valuable Pd(II) and Pt(II) ions in various catalytic applications.

One-step surfactant-free photoreduction synthesis of single-crystal silver triangular nanoprisms by surface modified chemically patterned ferroelectric crystals for SERS application

Anisotropic metal nanoparticles with plasmonic and photocatalytic action exhibit significant applications for SERS detection and green transformation. Current synthetic approaches using multiple chemicals cause substantial resource consumption and surface chemical residues that hinder analyte adsorption and thus prevent efficient action. Herein, we present a green production process using surface modified ferroelectric templates to grow triangular Ag nanoprisms for surface enhanced Raman spectroscopy (SERS). Surface modification of ferroelectric templates with positively charged ions suppresses the Ag nucleation on template surface and enables the reaction-controlled process to promote anisotropic photoreduction for the growth of Ag nanoprisms. Under optimal experimental conditions, numerous Ag nanoprisms with the (111) plane can be photoreduced with sharp tips and edges and greatly strengthen the excited electric field for Raman signal enhancement. The synthesized Ag nanoprism array presents superior SERS performance, including enhancement factor of 3.78 × 108, limit of detection as low as 4.95 × 10-9 M, and Raman signal enhancement by 8.63 times. The practical application of Ag nanoprisms is effectively demonstrated by the SERS detection of antibiotics. The reaction control by utilization of surface-modified ferroelectric templates provides a promising prospect for the green synthesis of anisotropic metal nanomaterials and the technical development of green applications.

Temperature indicator based on reshaping of silver nanoprisms

Silver nanoprisms exhibit fascinating optical properties, but they are thermodynamically unstable due to structural characteristics. Here, the intrinsic instability of Ag nanoprisms was utilized as a basis for developing a new sensing platform. When exposed to sodium bromide, the sharp tips of Ag nanoprisms were selectively damaged and Ag nanoprisms transformed into ellipsoid-shaped nanostructures. Due to these changes in shape, the localized surface plasmon resonance peaks of Ag nanoprism were tuned. Interestingly, the color change rate by NaBr introduction showed a strong correlation with the external temperature, which enabled us to develop a new type of colorimetric temperature indicator.

New electrode material integrates silver nanoprisms with phosphorus-doped carbon nanotubes for forensic detection of nitrite

A screen-printed carbon electrode (SPCE) was modified with a nanohybrid of silver (Ag) nanoprisms and phosphorus (P)-doped carbon nanotubes (AgNPr@P-CNT). The modified SPCE was coupled with a simple, portable flow system to produce an efficient amperometric sensor for the detection of nitrite ion (NO2−). P-doped CNTs were prepared via a one-pot solvothermal method and the P-CNTs were decorated with Ag nanoprisms synthesized by a one-pot chemical reduction method. The as-prepared AgNPr@P-CNT nanohybrid was thoroughly characterized. Energy-dispersive x-ray (EDX) analysis, Fourier transform infra‐red (FTIR), and Raman spectroscopy results confirmed the successful doping of CNTs with P atoms. Transmission electron microscopy (TEM) revealed the decoration of P-CNTs with triangular Ag nanoprisms measuring 25 ± 7 nm. In the optimal condition, the flow injection-amperometric sensor based on the developed AgNPr@P-CNT/SPCE exhibited suitable electrocatalytic activity toward NO2− oxidation. As a result, NO2− was detected with high sensitivity (0.73 µA µM−1 cm−2), a wide linear range (0.010–4000 µM), and a low limit of detection (0.0032 µM). The proposed sensing system was successfully applied to detect NO2− in gunshot residue samples, achieving good recoveries. The advantages of the proposed AgNPr@P-CNT nanohybrid can be applied in other electrochemical sensing applications.

Morphology transition of Ag nanoprisms as a platform to design a dual sensor for NADH sensitive assay

In the present study, we designed a dual colorimetric and fluorimetric probe based on Ag nanoprisms (AgNPRs) and rhodamine B (Rh B) for NADH analysis. AgNPRs/H2O2 were utilized as a colorimetric reporter (as well as fluorescence quencher) and Rh B was applied as a fluorimetric reporter. The colorimetric probe was developed based on the protecting effect of NADH on AgNPRs/H2O2 which caused a red shift in the surface plasmon resonance (SRP) peak of AgNPRs/H2O2. The observed red shift was proportional to the NADH concentration. On the other hand, the spectral overlap between excitation and emission of Rh B and absorption of AgNPRs/H2O2 in the presence and absence of NADH was different. As a result, the Rh B fluorescence emission, quenched by AgNPRs/H2O2 (due to IFE), was retrieved in the presence of NADH. These facts were employed to establish a dual colorimetric and fluorimetric probe to detect NADH at the range of 15–300 and 30–450 nM, respectively. Both - methods were successfully exploited to NADH assay in human serum samples.

Highly selective colorimetric sensing for iodide in water based on a novel surface passivation of Ag nanoprisms

Because silver (Ag) nanoprisms with sharp edges are inherently unstable, it is very important to develop a facile method that can dramatically improve the chemical stability of Ag nanoprisms while maintaining their inherent properties, including their plasmonic properties. In the present work, we developed a novel surface passivation method based on a single-step water-based process and showed that it significantly improved the chemical stability of Ag nanoprisms. Specifically, tetramethylethylenediamine (TMEDA) was used as an organic capping ligand, and the TMEDA-treated Ag nanoprisms retained their triangular shape even when exposed to various strong etchants including bromide, chloride, and hydrogen peroxide. Only in the presence of iodide did the sharp corners of the nanoprisms become spontaneously etched, and this etching resulted in a dramatic change in their localized surface plasmon resonance (LSPR) properties. The extent of the change of the LSPR properties depended on the concentration of iodide; hence, aqueous solutions of the TMEDA-treated Ag nanoprisms with different concentrations of iodide showed different colors. Based on this relationship, a colorimetric sensing probe that can detect iodide in aqueous solutions was developed. The sensing probe exhibited very high selectivity for iodide and the ability to determine the concentration of iodide over a wide range of concentrations. In addition, the probe was found to provide significant advantages over previously developed systems for iodide analysis, including portability, ease of use, point-of-care analysis, and naked-eye detection.

Hierarchically assembled silver nanoprism-graphene oxide-silicon nanowire arrays for ultrasensitive surface enhanced Raman spectroscopy sensing of atrazine

Exploration of novel strategies for fabricating SERS substrates attracted enormous research potential as achieving high sensitivity, reproducibility along with cost effectiveness is really challenging. Herein, we have fabricated hierarchical silver nanoprism/graphene oxide/silicon nanowire (Ag/GO/SiNWs) arrays as surface-enhanced Raman scattering (SERS) sensors for the effective detection of atrazine. Homogenous and vertically aligned SiNWs have been successfully synthesized using silver assisted chemical etching. Further, Ag/GO/SiNWs arrays were assembled by subsequent spin-coating of GO followed by drop-casting deposition of Ag nanoprisms. Micro-structural properties of as-fabricated nano-arrays have been well examined by scanning electron and atomic force microscopic techniques. Nanowire bunches have been decorated by GO layers; which further facilitates homogenous deposition of Ag nanoprisms. Using rhodamin 6G as probe molecule, high SERS activity and excellent reproducibility of as-fabricated substrates have been demonstrated. High efficiency of 3.2 × 108 and was obtained for the fabricated sensors; attributed to the synergetic charge transfer between GO and Ag nanoprisms on high surface area Si nanowires. Charge transfer mechanism that leading to enhanced surface plasmon resonance effect of the as-fabricated array was established as well. Further, these low cost Ag/GO/SiNWs sensors exhibited ultrasensitive detection of pollutants such as methylene blue and atrazine residues down to picomolar levels; these can serve as potential chemical sensors for rapid monitoring of environmental pollutants in trace levels.

A dual colorimetric and fluorometric sensor based on N, P-CDs and shape transformation of AgNPrs for the determination of 6-mercaptopurine

In this study, we designed a dual colorimetric and fluorometric sensor by using nitrogen and phosphor doped carbon dots (N, P-CDs) and Ag nanoprisms (AgNPrs) to detect 6-mercaptopurine (6-MP). For this purpose, we applied the AgNPrs/I- mixture to establish a shape transformation based colorimetric method for the detection of 6-MP. The assay mechanism of colorimetric method was based on etching and protecting effect of I- and 6-MP on the AgNPrs. In the presence of I-, as an etching agent, the solution color altered from blue to purple and the position of AgNPrs' local surface plasmon resonance (LSPR) peak shifted to the blue wavelengths. This phenomenon was assigned to the morphological change of AgNPrs. In the presence of 6-MP, AgNPrs were protected from etching by I-, so the LSPR peak position and solution color of AgNPrs remained unchangeable. Furthermore, the fluorescence intensity of N, P-CDs decreased with adding AgNPrs/I- due to the spectral overlap between etched AgNPrs and N, P-CDs. The CDs' quenched fluorescence was restored in the presence of 6-MP, as a result of the protecting effect of 6-MP on the AgNPrs. These facts have been applied to develop a dual sensor for the determination of 6-MP at the range of 10–500 nM and 30–500 nM by colorimetric and fluorometric detection methods. The detection limits were obtained 10 and 4 nM for fluorometric and colorimetric methods, respectively. The developed sensor was utilized for dual signal analysis of 6-MP in human serum samples with satisfactory results.

Enhancing the CO2-to-CO Conversion from 2D Silver Nanoprisms via Superstructure Assembly.

The electrochemical reduction of CO2 in a highly selective and efficient manner is a crucial step toward its reuse for the production of chemicals and fuels. Nanostructured Ag catalysts have been found to be effective candidates for the conversion of CO2-to-CO. However, the ambiguous determination of the intrinsic CO2 activity and the maximization of the density of exposed active sites have greatly limited the use of Ag toward the realization of practical electrocatalytic devices. Here, we report a superstructure design strategy prepared by the self-assembly of two-dimensional Ag nanoprisms for maximizing the exposure of active edge ribs. The vertically stacked Ag nanoprisms allow the exposure of >95% of the edge sites, resulting in an enhanced selectivity and activity toward the production of CO from CO2 with an overpotential of 152 mV. The Ag superstructures also demonstrate a selectivity of over 90% for 100 h together with a current retention of ≈94% at -600 mV versus the reversible hydrogen electrode and a partial energy efficiency for CO production of 70.5%. Our electrochemical measurements on individual Ag nanoprisms with various edge-to-basal plane ratios and the Ag superstructures led to the identification of the edge ribs as the active sites thanks to the ≈400 mV decrease in the onset potential compared to that of the Ag (111) basal planes and a turnover frequency of 9.2 × 10-3 ± 1.9 × 10-3 s-1 at 0 V overpotential.

Understanding radiative transitions and relaxation pathways in plexcitons

Summary Molecular aggregates on plasmonic nanoparticles have emerged as attractive systems for the studies of polaritonic light-matter states, called plexcitons. Such systems are tunable, scalable, easy to synthesize, and offer sub-wavelength confinement, all while giving access to the ultrastrong light-matter coupling regime, promising a plethora of applications. However, the complexity of these materials prevented the understanding of their excitation and relaxation phenomena. Here, we follow the relaxation pathways in plexcitons and conclude that while the metal destroys the optical coherence, the molecular aggregate coupled to surface processes significantly contributes to the energy dissipation. We use two-dimensional electronic spectroscopy with theoretical modeling to assign the different relaxation processes to either molecules or metal nanoparticle. We show that the dynamics beyond a few femtoseconds has to be considered in the language of hot electron distributions instead of the accepted lower and upper polariton branches and establish the framework for further understanding.

Enhancement of Raman Scattering and Exciton/Trion Photoluminescence of Monolayer and Few-Layer MoS2 by Ag Nanoprisms and Nanoparticles: Shape and Size Effects

The metal nanoparticle size and shape impact the plasmonic enhancement of Raman and photoluminescence (PL) spectra of monolayer and few-layer MoS2 decorated with them. The plasmonic enhancement is investigated for Ag nanotriangles (NTs or nanoprisms) of different sizes in comparison to Ag nanospheres (NSs) at room temperature. After the decoration with Ag NTs, the intensity of both Raman modes of MoS2 increases up to 6.8 times. The μ-PL spectra of bare MoS2 show the presence of the A and B exciton bands as well as of a weak trion component. After covering the flakes with 50 nm Ag NTs, the highest integrated PL enhancement factors are 2.9 and 2.1 under 532 and 405 nm excitations, respectively. The revealed shape effect is that Ag NTs provide much stronger Raman and exciton emission enhancement than Ag NSs, which is due to the generation of plasmonic hot spots near the sharp edges and tips of NTs. Another mechanism of enhancement is the plasmonic coupling between the neighboring Ag NTs that causes the generation of hot spots in the gap between NTs. The revealed size effect is a decrease of Raman and PL enhancement with an increase in size of Ag NTs or NSs, which is due to an increase in radiative damping of plasmon oscillation occurring with an increase in nanoparticle size. The important feature is a strong enhancement of the A– trion component after decorating MoS2 with Ag nanoparticles. The phenomenon may be explained by the surface-plasmon-mediated generation of hot electrons in Ag nanostructures, which then inject to MoS2 flakes. This work gives new fundamental insights into the physical mechanisms of light–matter coupling in hybrid two-dimensional (2D) semiconductor/plasmonic nanoparticle structures, which are highly promising for next-generation optoelectronic and nanophotonic devices.

Detection of multi-class pesticide residues with surface-enhanced Raman spectroscopy

The excessive use of pesticides disturbs the natural balance in the environment, creates resistance to pesticides and leads to water and food contamination. Therefore, the implementation of fast, robust and cost effective techniques for the monitoring of pesticides is required. In this work surface-enhanced Raman spectroscopy (SERS) was used for the detection of four common pesticides: atrazine, simazin, irgarol, and diuron. SERS is nowadays considered an effective technique for detection of various analytes in low concentration. Sensitivity of the SERS method depends on the type of substrate that can be either a colloidal solution of metal nanoparticles (NPs) or a metal surface with a suitable nanostructured topology. Here, we have investigated the application of silver nanospheres and silver nanoprisms as SERS substrates in pesticides detection. Colloids with spherical NPs were produced by chemical reduction while Ag nanoprisms were prepared by reducing silver nitrate with borohydride (with citrate as a stabilizing agent) and stirring under a UV lamp for 4 and 10 h. The SERS results have shown that, in the presence of synthesized NPs, it was possible to detect millimolar concentrations of aforementioned pesticides with the exception of diuron.

Plasmonic triangular nanoprism sensors

This review gives a one-stop account of LSPR sensors using Au and Ag nanoprisms from basic physics to recent applications.

Strong coupling with absorption and emission features of Ag@Au hollow nanoshells interacting with J-aggregated dye molecules

We investigate the strong coupling from 5,5’,6,6’-tetrachloro-1,1’-diethyl-3,3’-di(4-sulfobutyl)-benzimidazolocarbocyanine (TDBC) molecules near pure nano-triangular Ag prisms or Ag@Au hollow nanoshells. When TDBC molecules are deposited on pure Ag nanoprisms or Ag@Au hollow nanoshells with the plasmonic resonance peak, matching very closely with the absorption band of TDBC J-aggregates, obvious Rabi splitting can be observed due to the strong coupling regime. Meanwhile, the photoluminescence intensity decreased with the increasing of the temperature, verifying the decreasing plasmon–exciton coupling interaction in the higher temperature. Our experimental results are coincident with the simulation results calculated by finite-difference time-domain method.

Core–Shell Bimetallic Nanoparticle Trimers for Efficient Light-to-Chemical Energy Conversion

Incorporation of catalytically active materials into plasmonic metal nanostructures can efficiently merge the reactivity and energy harvesting abilities of both types of materials for visible light photocatalysis. Here we explore the influence of electromagnetic hotspots in the ability of plasmonic core-shell colloidal structures to induce chemical transformations. For this study, we developed a synthetic strategy for the fabrication of Au nanoparticle (NP) trimers in aqueous solution through fine controlled galvanic replacement between Ag nanoprisms and Au precursors. Core-shell Au@M NP trimers with catalytically active metals (M = Pd, Pt) were subsequently synthesized using Au NP trimers as templates. Our experimental and computational results highlight the synergy of geometry and composition in plasmonic catalysts for plasmon-driven chemical reactions.

Structural Study of the Photo-Mediated Growth of Silver Nanoprisms.

We present a small-angle X-ray scattering (SAXS) study of the anisotropic photoinduced growth of silver (Ag) nanoprisms in aqueous dispersions. The growth of nearly spherical (<10 nm) Ag particles into large (>40 nm) and thin (<10 nm) triangular nanoprisms induced by 550 nm laser is followed in terms of particle size using indirect and direct methods for irradiation times up to 150 min. During the process, the surface-to-volume ratio of the particles decreased. The SAXS data of the initial solution fit well to the model of polydisperse spheres with pronounced average diameters around 7.4 nm and 10 nm. The data after 45 min irradiation fit well to the model containing approximately the same amount of the initial particles and the end product, the nanoprisms.

Photomodulated Spatially Confined Chemical Reactivity in a Single Silver Nanoprism

Single-atom and single-particle catalysis is an area of considerable topical interest due to their potential in explaining important fundamental processes and applications across several areas. An interesting avenue in single-particle catalysis is spatial control of chemical reactivity within the particle by employing light as an external stimulus. To demonstrate this concept, we report galvanic replacement reactions (GRRs) as a spatial marker of subparticle chemical reactivity of a silver nanoprism with AuCl4- ions under optical excitation. The location of a GRR within a single Ag nanoprism can be spatially controlled depending on the plasmon mode excited. This leads to chemomorphological transformation of Ag nanoprisms into interesting Ag-Au structures. This spatial biasing effect is attributed to localized hot electron injection from the tips and edges of the silver nanoprisms to the adjacent reactants that correlate with excitation of different surface plasmon modes. The study also employs low-energy-loss EELS mapping to additionally probe the spatially confined redox reaction within a silver nanoprism. The findings presented here allow the visualization of a plasmon-driven subparticle chemical transformation with high resolution. The selective optical excitation of surface plasmon eigenmodes of anisotropic nanoparticles offers opportunities to spatially modulate chemical transformations mediated by hot electron transfer.

Solid-phase colorimetric sensing probe for bromide based on a tough hydrogel embedded with silver nanoprisms

Sharp-tipped anisotropic silver (Ag) nanostructures are attracting increasing attention because of their unusual optical properties. However, the sharp tips make such nanostructures thermodynamically unstable; thus, they have been considered unsuitable for use in colorimetric sensing because of their tendency to aggregate or transform in a solution state. In the present study, a colorimetric sensing platform for detecting bromide (Br−) in an aqueous medium was developed. The platform is based on the localized surface plasmon resonance (LSPR) properties of Ag nanoprisms with sharp tips. The key to using such Ag nanocrystals with extreme anisotropic structures is to adopt a solid-phase sensing platform. A Ag-nanoprism-embedded tough hydrogel with interpenetrating polymer networks was synthesized via aqueous-phase polymerization and crosslinking processes. The Ag nanoprisms immobilized inside the hydrogel were stable and did not exhibit aggregation or degradation over time; specifically, when the hydrogel was dried, the nanoprisms retained their inherent LSPR properties for an extended period. By taking advantage of the rapid and spontaneous morphological transformation of Ag nanoprisms inside the hybrid hydrogel exposed to Br− and the corresponding changes in their LSPR properties, we designed a plasmonic sensing platform for the sensitive and selective detection of Br− in an aqueous medium. The proposed colorimetric sensing platform was found to exhibit a wide sensing range and high selectivity, with a low limit of detection (LOD) of 10 μM, and offers substantial advantages over previously developed systems; specifically, it is portable, eco-friendly, safe to use and handle, stable for extended periods, and enables naked-eye detection. We believe that the as-proposed sensing platform can be used as a point-of-care analytical tool for detecting Br− in a broad range of samples.

Etching-controlled suppression of fluorescence resonance energy transfer between nitrogen-doped carbon dots and Ag nanoprisms for glucose assay and diabetes diagnosis.

Numerous methods have been developed for glucose detection, only few cases can be really applied in clinical diagnosis. Herein, we report a new approach to achieve the detection of glucose in clinical samples and distinguishing the diabetic patients with healthy ones. Specifically, a fluorescence resonance energy transfer (FRET) system is established first, where nitrogen-doped carbon dots (N-CDs) and Ag nanoprisms (AgNPRs) with good spectral overlap act as energy donor and acceptor, respectively. Then, the FRET can be inhibited through oxidative etching of the energy acceptor in the presence of glucose and glucose oxidase, where hydrogen peroxide is generated to transform AgNPRs into Ag+ ions. Based on the turn-on fluorescent signal versus glucose concentration, a new method for quantitative detection of glucose is developed. This etching-induced analytical method is simple, reliable, robust and cost-effective, which is promising to assist the doctors to clinically diagnose diabetes and other diseases related to metabolic disorders.

NIR-II driven plasmon-enhanced cascade reaction for tumor microenvironment-regulated catalytic therapy based on bio-breakable Au–Ag nanozyme

Emerging nanozymes with natural enzyme-mimicking catalytic activities have inspired extensive research interests due to their high stability, low cost, and simple preparation, especially in the field of catalytic tumor therapy. Here, bio-breakable nanozymes based on glucose-oxidase (GOx)-loaded biomimetic Au–Ag hollow nanotriangles (Au–Ag–GOx HTNs) are designed, and they trigger an near-infrared (NIR)-II-driven plasmon-enhanced cascade catalytic reaction through regulating tumor microenvironment (TME) for highly efficient tumor therapy. Firstly, GOx can effectively trigger the generation of gluconic acid (H+) and hydrogen peroxide (H2O2), thus depleting nutrients in the tumor cells as well as modifying TME to provide conditions for subsequent peroxidase (POD)-like activity. Secondly, NIR-II induced surface plasmon resonance can induce hot electrons to enhance the catalytic activity of Au–Ag–GOx HTNs, eventually boosting the generation of hydroxyl radicals (•OH). Interestingly, the generated H2O2 and H+ can simultaneously induce the degradation of Ag nanoprisms to break the intact triangle nanostructure, thus promoting the excretion of Au–Ag–GOx HTNs to avoid the potential risks of drug metabolism. Overall, the NIR-II driven plasmon-enhanced catalytic mechanism of this bio-breakable nanozyme provides a promising approach for the development of nanozymes in tumor therapy.