Metal Nanoparticles Research Articles

Ultrafast Laser Manipulation of In-Lattice Plasmonic Nanoparticles.

Plasmonic nanoparticles enable manipulation and enhancement of light fields at deep subwavelength scales, leading to structures and devices for diverse applications in optics. Despite hybrid plasmonic materials display remarkable optical properties due to interactions between components in nanoproximity, scalable production of plasmonic nanostructures within a single-crystalline matrix to achieve an ideal plasmon-crystal interface remains challenging. Here, a novel approach is presented to realize efficient manipulation of in-lattice plasmonic nanoparticles. Employing ultrafast-laser-driven plasmonic nanolithography, metallic nanoparticles with controllable morphology are precisely defined in the crystalline lattice of yttrium aluminum garnet (YAG) crystal. Through direct ion implantation, hybrid plasmonic material composed of nanoparticles embedded in a sub-surface amorphous YAG layer is created. Subsequently, femtosecond laser pulses guide formation and reshaping of plasmonic nanoparticles from the amorphous layer into the single-crystalline matrix along direction of light propagation, facilitated by a plasmon-mediated evolution of laser energy deposition. By tailoring resonance modes and optimizing the coupling between structured particle assemblies, a range of applications including polarization-dependent absorption and nonlinearity, controllable photoluminescence, and structural color generation is demonstrated. This research introduces a new approach for fabricating advanced optical materials featuring in-lattice plasmonic nanostructures, paving the way for the development of diverse functional photonic devices.

Molten Salt Derived MXenes: Synthesis and Applications.

About one decade after the first report on MXenes, these 2D early transition metal carbides or nitrides have become among the best-performing materials in electrode applications related to electrical energy storage devices and power-to-fuels conversion. MXenes are obtained by a top-down approach starting from the appropriate 3D MAX phase that undergoes etching of the A-site metal. Initial etching procedures are based on the use of concentrated HF or the in situ generation of this highly corrosive and poisonous reagent. Etching of the MAX phase is one of the major hurdles limiting the progress of the field. The present review summarizes an alternative, universal, and easily scalable etching procedure based on treating the MAX precursor with a Lewis acid molten salt. The review starts with presenting the current state of the art of the molten salt etching procedure to obtain or modify MXene, followed by a summary of the applications of these MXene samples. The aim of the review is to show the versatility and advantages of molten salt etching in terms of general applicability, control of the surface terminal groups, and uniform deposition of metal nanoparticles, among other features of the procedure.

Helical Hybrid Nanostructure Based on Chiral M13 Bacteriophage via Evaporation-Induced Three-Dimensional Process

The use of naturally sourced organic materials with chirality, such as the M13 bacteriophage, holds intriguing implications, especially in the field of nanotechnology. The chirality properties of bacteriophages have been demonstrated through numerous studies, particularly in the analysis of liquid crystal phase transitions, developing specific applications. However, exploring the utilization of the M13 bacteriophage as a template for creating chiral nanostructures for optics and sensor applications comes with significant challenges. In this study, the chirality of the M13 bacteriophage was leveraged as a valuable tool for generating helical hybrid structures by combining it with nanoparticles through an evaporation-induced three-dimensional (3D) printing process. Utilizing on the self-assembly property of the M13 bacteriophage, metal nanoparticles were organized into a helical chain under the influence of the M13 bacteriophage at the meniscus interface. External parameters, including nanoparticle shape, the ratio between the bacteriophage and nanoparticles, and pulling speed, were demonstrated as crucial factors affecting the fabrication of helical nanostructures. This study aimed to explore the potential of chiral nanostructure fabrication by utilizing the chirality of the M13 bacteriophage and manipulating external parameters to control the properties of the resulting hybrid structures.

Strong Interaction between Molybdenum Compounds and Mesoporous CMK‐5 Supports Boosts Hydrogen Evolution Reaction

AbstractStrong metal‐support interaction (SMSI) between transition metal nanoparticles and carbon matrix offers significant structure advantages due to the ability to modulate the electronic structure of metal nanoparticles, increase the density of active sites, and improve the conductivity of catalysts. Here, ultrafine nanoparticles of metallic molybdenum compounds (MoP, Mo2C, and MoS2) strongly coupled with mesoporous carbon CMK‐5 are synthesized. The confinement growth of nanoparticles in the pores of CMK‐5 produces encapsulated nanoparticles, affording facilitated electron transfer, and enhancing the HER activity induced by the SMSI effect. The hierarchical nanostructure and strong electronic interactions between the carbon substrate and molybdenum‐based nanoparticles allow efficient mass/electron transport between the carbon substrate and molybdenum‐based nanoparticles, improving the catalytic hydrogen evolution reaction (HER) activity. The effective electron exchange between the Mo species and the CMK‐5 support is studied by X‐ray photoelectron spectroscopy (XPS) measurement, confirming the presence of the SMSI effect. The resulting MoP/CMK‐5 catalyst exhibits outstanding HER performance in alkaline (65 mV@10 mA cm−2), acidic (123 mV@10 mA cm−2), and simulated seawater electrolytes (103 mV@10 mA cm−2), making it one of the most promising catalysts reported for HER. This work provides guidance on designing high‐performance electrocatalysts with SMSI for the enhancement of the electrochemical reaction.

Biosynthesis of Silver and Gold Nanoparticles Using Geum urbanum L. Rhizome Extracts and Their Biological Efficiency

AbstractThe present study evaluates the biosynthesis of AgNPs and AuNPs using aqueous and ethanolic Geum urbanum L. rhizome extracts. The biosynthesized metal nanoparticles (MNPs) were characterized using UV-Vis spectroscopy, FTIR, DLS, SEM, EDX, and TEM. The UV-Vis spectra confirmed the synthesis of AgNPs and AuNPs through peaks corresponding to the surface plasmon effect of metallic Ag (400–430 nm) and Au (530–570 nm). FTIR analysis indicated that alcohols, phenols, proteins, and carbohydrates from G. urbanum rhizome extracts composition are involved in MNPs synthesis. In DLS analysis, AgNPs (34.26–41.14 nm) showed smaller hydrodynamic diameters than AuNPs (46.26–70.29 nm). At the same time, all values for zeta potential were negative, between − 21 and − 13 mV, suggesting good stabilities for all the colloidal MNPs systems in dispersion. TEM analysis showed that the biosynthesized AgNPs had a spherical morphology, while AuNPs were quasi-spherical, polygonal, and triangular. According to TEM data, AgNPs synthesized using aqueous and ethanolic G. urbanum rhizome extracts were characterized by mean diameters of 9.82 ± 3.68 and 14.29 ± 3.46 nm, while AuNPs by 15.88 ± 6.28 and 24.89 ± 10.75 nm, respectively. EDX analysis confirmed the presence of metallic Ag and Au in the MNPs composition by detecting strong signals at 3 (AgNPs) and 2.2 keW (AuNPs). In disc diffusion assay, MNPs showed good antimicrobial activity against Gram-positive (S. aureus MSSA, S. aureus MRSA, S. epidermidis) and Gram-negative (E. coli, P. aeruginosa, K. pneumoniae) bacteria and yeasts (C. albicans). AgNPs and AuNPs were also characterized by a significant antioxidant potential, evaluated through in vitro assays (lipoxygenase inhibition, DPPH radical scavenging activity, metal ion chelating activity, and hydroxyl radical scavenging assays). An overall better activity was obtained for the ethanolic G. urbanum rhizome extract and its derived AgNPs (EC50 = 34.2 ± 1.86 mg/mL in lipoxygenase inhibition assay). Therefore, the G. urbanum rhizome extracts proved to be excellent sources for biologically active AgNPs and AuNPs.

Influence of metal and metal oxide nanoparticles on growth and total phenolic content accumulation of Anoectochilus roxburghii cultured in vitro

The application of metal nanoparticles in agriculture and related fields, especially in plant cell tissue culture has increased interest in recent years due to its potential benefits. This study used gold nanoparticles (AuNPs), silver nanoparticles (AgNPs), copper nanoparticles (CuNPs) and magnetite nanoparticles (Fe3O4NPs) to evaluate their effect on the growth and total phenolic content (TPC) of Anoectochilus roxburghii. The results showed that Fe3O4 NPs were the most positively influenced metal nanoparticles in increasing biomass and TPC of A. roxburghii among metal nanoparticles tested. After 8 weeks of culture, the dry weight (DW) and TPC of the plants cultured on the medium containing 5 ppm Fe3O4NPs were 39.07 mg and 13.0 mg gallic acid respectively per g of dry weight (mg GAE/g DW). Meanwhile, on the medium without Fe3O4NPs, they were 30.47 mg and 6.71 mg GAE/g DW respectively. This study proposed an effective approach to improve the growth and accumulation of TPC in A. roxburghii. Moreover, it suggests the potential application of metal nanoparticles in plant tissue culture and the production of bioactive compounds.

Stimuli-Responsive Release-Active Dressing: A Promising Solution for Eradicating Biofilm-Mediated Wound Infections.

Biofilm-mediated wound infections pose a significant challenge due to the limitations of conventional antibiotics, which often exhibit narrow-spectrum activity, fail to eliminate recurrent bacterial contamination, and are unable to penetrate the biofilm matrix. While the search for alternatives has explored the use of metal nanoparticles and synthetic biocides, these solutions often suffer from unintended toxicity to surrounding tissues and lack controlled administration and release. In this study, we engineered a pH-responsive release-active dressing film based on carboxymethyl cellulose, incorporating a synthetic antibacterial molecule (SAM-17). The dressing film exhibited optimal mechanical stability for easy application and demonstrated excellent fluid absorption properties, allowing for prolonged moisturization at the site of injury. The film exhibited pH-dependent release of cargo, with 78% release within 24 h at acidic pH, enabling targeted antibacterial drug delivery within the wound microenvironment. Furthermore, the release-active film effectively eliminated repeated challenges of bacterial contamination. Remarkably, the film demonstrated a minimal toxicity profile in both in vitro and in vivo models. The film eliminated preformed bacterial biofilms, achieving a reduction of 2.5 log against methicillin-resistant Staphylococcus aureus (MRSA) and 4.1 log against vancomycin-resistant S. aureus (VRSA). In a biofilm-mediated MRSA wound infection model, this release-active film eradicated the biofilm-embedded bacteria by over 99%, resulting in accelerated wound healing. These findings highlight the potential of this film as an effective candidate for tackling biofilm-associated wound infections.

Electric and dielectric responses of Au/n-Si structure by Mn doped PVC interfacial layers

This paper has investigated and compared the impact of polyvinyl chloride (PVC) without/with manganese (Mn) metallic nanoparticles interfacial layer on the electric and impedance characteristics of Schottky diode (SD) with a structure of Au/n-Si (MS). The structures of these two metal-polymer-semiconductor (MPS) SDs are Au/PVC/n-Si and Au/PVC:Mn/n-Si. A detailed description of the SDs manufacturing process is given. The x-ray diffraction (XRD) analysis, Scanning Electron Microscope (FE-SEM) images, and Electron Dispersive x-ray (EDX) spectroscopy are three methods that have been utilized to examine mean size of crystallite, morphology of surface, purity specification. The fundamental electronic variables of these devices are ascertained and contrasted with one another using the I-V characteristic measurement at ±6 V. Ohm’s law, Thermionic Emission (TE) theory, modified Norde, and Cheung functions are used to calculate the SDs’ leakage current (I0), ideality coefficient (n), potential barrier height (BH), shunt (Rsh), and series (Rs) resistances. Investigations are conducted on the energy dependence of surface states density (Nss) and the current conduction mechanisms (CCMs) for both reverse and forward biases. These interfacial layers are known to decrease the n, Rs, and Nss. The PVC polymer interlayer leads to improve the efficiency of the MS-type SD, but it does not when doped by Mn nanoparticles. Additionally, by measuring impedance at a bias of 1.5 V and 100 Hz-1 MHz frequency range, the frequency dependence of dielectric properties of the prepared SDs is studied. The dielectric permittivity, dielectric loss tangent, electronic modulus, and ac electronic conductivity of these SDs are all studied.

Synthesis of Metallic and Metal Oxide Nanoparticles Using Homopolymers as Solid Templates: Luminescent Properties of the Eu+3 Nanoparticle Products

Starting from poly(4-vinylpyridine) ((P4VP)n), poly(2-vinylpyridine) ((P2VP)n), and [N=P(O2CH2CF3)]m-b-P2VP20 block copolymers, a series of metal-containing homopolymers, (P4VP)n⊕MXm, (P2VP)n⊕MXm, and [N=P(O2CH2CF3)]m-b-P2VP20]⊕MXm MXm = PtCl2, ZnCl2, and Eu(NO3)3, have been successfully prepared by using a direct and simple solution methodology. Solid-state pyrolysis of the prepared metal-containing polymeric precursors led to the formation of a variety of different metallic and metal oxide nanoparticles (Pt, ZnO, Eu2O3, and EuPO4) depending on the composition and nature of the polymeric template precursor. Thus, whereas Eu2O3 nanostructures were obtained from europium-containing homopolymers ((P4VP)n⊕MXm and (P2VP)n⊕MXm), EuPO4 nanostructures were achieved using phosphorus-containing block copolymer precursors, [N=P(O2CH2CF3)]m-b-P2VP20]⊕MXm with MXm = Eu(NO3)3. Importantly, and although both Eu2O3 and EuPO4 nanostructures exhibited a strong luminescence emission, these were strongly influenced by the nature and composition of the macromolecular metal-containing polymer template. Thus, for P2VP europium-containing homopolymers ((P4VP)n⊕MXm and (P2VP)n⊕MXm), the highest emission intensity corresponded to the lowest-molecular-weight homopolymer template, [P4VP(Eu(NO3)3]6000, whereas the opposite behavior was observed when block copolymer precursors, [N=P(O2CH2CF3)]m-b-P2VP20]⊕MXm MXm= Eu(NO3)3, were used (highest emission intensity corresponded to [N=P(O2CH2CF3)]100-b-[P2VP(Eu(NO3)3)x]20). The intensity ratio of the emission transitions: 5D0 → 7F2/5D0 → 7F1, suggested a different symmetry around the Eu3+ ions depending on the nature of the polymeric precursor, which also influenced the sizes of the prepared Pt°, ZnO, Eu2O3, and EuPO4 nanostructures.

Deciphering the Mechanisms and Biotechnological Implications of Nanoparticle Synthesis Through Microbial Consortia.

Nanomaterial synthesis is a growing study area because of its extensive range of uses. Nanoparticles' high surface-to-volume ratio and rapid interaction with various particles make them appealing for diverse applications. Traditional physical and chemical methods for creating metal nanoparticles are becoming outdated because they involve complex manufacturing processes, high energy consumption, and the formation of harmful by-products that pose major dangers to human health and the environment. Therefore, there is an increasing need to find alternative, cost-effective, dependable, biocompatible, and environmentally acceptable ways of producing nanoparticles. The process of synthesizing nanoparticles using microbes has become highly intriguing because of their ability to create nanoparticles of varying sizes, shapes, and compositions, each with unique physicochemical properties. Microbes are commonly used in nanoparticle production because they are easy to work with, can use low-cost materials, such as agricultural waste, are cheap to scale up, and can adsorb and reduce metal ions into nanoparticles through metabolic activities. Biogenic synthesis of nanoparticles provides a clean, nontoxic, ecologically friendly, and sustainable method using renewable ingredients for reducing metals and stabilizing nanoparticles. Nanomaterials produced by bacteria can serve as an effective pollution control method due to their many functional groups that can effectively target contaminants for efficient bioremediation, aiding in environmental cleanup. At the end of the paper, we will discuss the obstacles that hinder the use of biosynthesized nanoparticles and microbial-based nanoparticles. The paper aims to explore the sustainability of microorganisms in the burgeoning field of green nanotechnology.

Antimicrobial Activity of Green Synthesized Silver and Copper Oxide Nanoparticles against the Foodborne Pathogen Campylobacter jejuni

Campylobacter jejuni is a major cause of global foodborne illnesses. To develop alternative antimicrobial strategies against C. jejuni, this study designed and optimized the green synthesis of metallic nanoparticles (NPs) with intracellular components of the medicinal fungus Ganoderma sessile to provide the needed reducing and stabilizing agents. NPs were characterized by transmission electron microscopy and dynamic light scattering, and the quasi-spherical NPs had sizes of 2.9 ± 0.9 nm for the copper oxide NPs and 14.7 ± 0.6 nm for the silver NPs. Surface charge assessment revealed zeta potentials of −21.0 ± 6.5 mV and −24.4 ± 7.9 mV for the copper oxide and silver NPs, respectively. The growth inhibition of C. jejuni by the NPs occurred through attachment to the outer cell membrane and subsequent intracellular internalization and resulted in minimum inhibitory concentrations of the silver NPs at 6 µg/mL and copper oxide NPs at 10 µg/mL. On the other hand, a differential ROS production caused by silver and copper NPs was observed. In summary, this research presents the first demonstration of using green synthesis with the medicinal fungus G. sessile to produce metallic NPs that effectively inhibit C. jejuni growth, providing a sustainable and effective approach to the traditional use of antimicrobials.

An acoustofluidic picoinjector

Droplet microfluidics has emerged as a valuable technology for a multitude of chemical and biomedical applications, offering the capability to create independent microenvironments for high-throughput assays. Central to numerous droplet microfluidic applications is the picoinjection of materials into individual droplets, yet existing picoinjection methods often exhibit high power requirements, lack biocompatibility, and/or suffer from limited controllability. Here, we present an acoustofluidic picoinjector that generates acoustic pressure at the droplet interface to enable on-demand, energy-efficient, and biocompatible injection at high precision. We validate our platform by performing acid-base titrations by iteratively injecting picoliter volume reagents into droplets to induce pH transitions detectable by color change in solution. Additionally, we demonstrate the versatility of the acoustofluidic picoinjector in the synthesis of metallic nanoparticles, yielding highly monodisperse and reproducible particle morphologies compared to conventional bulk-phase techniques. By facilitating controlled delivery of reagents or biological samples with unparalleled accuracy, acoustofluidic picoinjection broadens the utility of droplet microfluidics for a myriad of applications in chemical and biological research.

High-strength and impermeable sapphire/aluminum joints fabricated by ultrafast laser microwelding: Microstructures and joining mechanism

In this work, robust joints of sapphire and aluminum were successfully achieved by direct ultrafast laser transmission microwelding. Effects of laser parameters on the microstructures and mechanical properties were comprehensively studied. The welding process highly depended on the laser ablated metal nanoparticles within the heterojunction, as well as the thermal accumulation under multiple laser pulses irradiation. It showed that lack of fusion at the sapphire/aluminum interface can occur due to the incomplete melting of ablated nanoparticles at low laser fluence (<0.48 J/cm2). While serious cavities and cracks inside the brittle sapphire were formed with the intensified stress concentration after melting-solidification process at excessive laser fluence (>0.64 J/cm2). A nearly defect-free joint was obtained with max. shear strength of 128.1 ± 8.2 MPa at room temperature, when the laser fluence was 0.56 J/cm2. The high shear strength can be attributed to the tortuous interface with wide elemental transition layer. Meanwhile, the welded sapphire/aluminum joints exhibited high reliability under extreme service temperatures, which the shear strength can reach 159.8 ± 8.96 MPa at −50 °C and 80.6 ± 11.1 MPa at 200 °C. The sealing tests also showed the excellent impermeability of laser welded sapphire/aluminum structure, confirming the micro-crack free joint formation. This work demonstrates the feasibility of using ultrafast laser to achieve high-quality sapphire/aluminum joint, which is promising in heat-dissipation substrate manufacturing in power semiconductor devices.

New Insights into Materials for Pesticide and Other Agricultural Pollutant Remediation

The increase in the world population and the intensification of agricultural practices have resulted in the release of several contaminants into the environment, especially pesticides and heavy metals. This article reviews recent advances in using adsorbent and catalytic materials for environmental decontamination. Different materials, including clays, carbonaceous, metallic, polymeric, and hybrid materials, are evaluated for their effectiveness in pollutant removal. Adsorption is an effective technique due to its low cost, operational simplicity, and possibility of adsorbent regeneration. Catalytic processes, especially those using metallic nanoparticles, offer high efficiency in degrading complex pesticides. Combining these technologies can enhance the efficiency of remediation processes, promoting a more sustainable and practical approach to mitigate the impacts of pesticides and other agricultural pollutants on the environment. Therefore, this review article aims to present several types of materials used as adsorbents and catalysts for decontaminating ecosystems affected by agricultural pollutants. It discusses recent works in literature and future perspectives on using these materials in environmental remediation. Additionally, it explores the possibilities of using green chemistry principles in producing sustainable materials and using agro-industrial waste as precursors of new materials to remove contaminants from the environment.

Antibacterial Mechanism of d-Cysteine/Polyethylene Glycol-Functionalized Gold Nanoparticles and Their Potential for the Treatment of Bacterial Infections.

Bacterial infection has always posed a severe threat to public health. Gold nanoparticles (Au NPs) exhibit exceptional biocompatibility and hold immense potential in biomedical applications. However, their antibacterial effectiveness is currently unsatisfactory. Herein, a chiral antibacterial agent with high stability was prepared by the modification of Au NPs with d-cysteine with the assistance of polyethylene glycol (PEG). The as-synthesized d-cysteine/PEG-Au NPs (D/P-Au NPs) exhibited a stronger (99.5-99.9%) and more stable (at least 14 days) antibacterial performance against Gram-negative (Escherichia coli and Listeria monocytogenes) and Gram-positive (Salmonella enteritidis and Staphylococcus aureus) bacteria, compared with other groups. The analysis of the antibacterial mechanism revealed that the D/P-Au NPs mainly affected the assembly of ribosomes, the biosynthesis of amino acids and proteins, as well as the DNA replication and mismatch repair, ultimately leading to bacterial death, which is significantly different from the mechanism of reactive oxygen species-activated metallic antibacterial NPs. In particular, the D/P-Au NPs were shown to effectively accelerate the healing of S. aureus-infected wounds in mice to a rate comparable to or slightly higher than that of vancomycin. This work provides a novel approach to effectively design chiral antibacterial agents for bacterial infection treatment.

RuNi/TiZr-MMO Catalysts Derived from Zr-Modified NiTi-LDH for CO-Selective Methanation

CO-selective methanation (CO-SMET) is an efficient hydrogen-rich (H2-rich) gas purification technology for proton exchange membrane fuel cells. It is vital to develop suitable catalysts with good low-temperature activity for CO-SMET reactions. In this study, RuNi/TiZrx-mixed metal oxide (RuNi/TiZrx-MMO) catalysts with different molar ratios of Zr/Ti, derived from a Zr-promoted NiTi-layered double hydroxide (NiTi-LDH) precursor were successfully prepared using the co-precipitation and wet impregnation methods. The RuNi/TiZr0.2-MMO catalyst possesses higher catalytic performance in a lower temperature window of 180–280 °C, which can reduce the CO concentration to be below 10 ppm. The characterization results obtained from XRD, BET, SEM, TEM, XPS, TPR, and TPD suggest that the addition of ZrO2 increases the surface area of the catalyst, improves the dispersion of metallic nanoparticles, increases the reducibility of Ni species on the RuNi/TiZr0.2-MMO catalyst’s surface, and enhances the adsorption and activation ability of CO, resulting in remarkable catalytic performance at lower reaction temperatures. Moreover, the RuNi/TiZr0.2-MMO catalyst demonstrated long-term catalytic stability and carbon resistance.

Large-scale growth of MoS2 hybrid layer by chemical vapor deposition with nanosheet promoter

Molybdenum disulfide (MoS2) serves as the representative transition metal dichalcogenide material, showing promise for diverse applications owing to its outstanding properties. Extensive research has been conducted on the growth of large-scale MoS2 films using chemical vapor deposition (CVD) with seeding accelerators for various device applications. In this study, we investigated the growth of large-scale MoS2 films for potential applications, in which our approach utilized CVD with a homogeneous nanosheet promoter (MoS2 flakes) and effectively minimized residue creation. Optical and structural analyses confirmed the successful synthesis of a large-scale MoS2 layer. Moreover, the decoration of metallic nanoparticles on the MoS2 surface was employed to enhance the functionalities of application devices such as optical sensors and gas sensors. The capability of MoS2 to act as a nucleation site for nanoparticles during synthesis offered an intriguing pathway for augmenting the attachment and performance of nanoparticles on the MoS2 surface. The photodetector, integrating a hybrid MoS2 layer and Cu nanoparticles, exhibited superior photodetection properties, attributed to the increased excitons at the interface between the metal electrodes and MoS2 films. Furthermore, in order to enhance the characteristics of the gas sensor, Pd nanoparticles were incorporated during the synthesis of MoS2 layers. This dynamic interface between Pd particles and MoS2 films presents an opportunity to explore novel materials with enhanced catalytic properties.

Au nanoparticles decorated graphitic carbon nitride nanosheets as a sensitive and selective fluorescence probe for Fe3+ and dichromate ions in aqueous medium

Graphitic carbon nitride mutated with metal nanoparticles has captivated great interest as an effective fluorescent sensor for the detection of harmful ions present in water. In the present work, bulk-gCN was synthesized using melamine as precursor, and further Au-gCN nanocomposite were fabricated via in-situ direct reduction deposition method. The structural, morphological, compositional, stability and optical properties of bulk gCN and Au-gCN nanocomposite were examined using various scattering and spectroscopic techniques such as HRTEM, XPS, XRD and SEM. The synthesized bulk gCN straggles during selectivity studies with different cations and anions because of its uneven surface morphology, however in Au-gCN gold nanoparticles are uniformly distributed on the gCN sheets which results in its enhanced selectivity over bulk gCN. This leads to the fabrication of an optical sensor for Fe3+ and Cr2 ions with limit of detection of 4.62 and 2.77 μM, respectively. The sensing of Fe3+ ions corresponds to the photoinduced electron transfer (PET) mechanism, while the detection of chromate species is associated with an inner filter effect (IFE). The practical applicability of the sensor was also evaluated for different environmental water samples. The high stability, sensitivity, and specificity of Au-gCN nanocomposite make it a potential fluorescent probe for Fe3+ and Cr2 ions in water samples.

Polyoxometalate-HKUST-1 composite derived nanostructured Na-Cu-Mo2C catalyst for efficient reverse water gas shift reaction.

Transforming CO2 to CO via reverse water-gas shift (RWGS) reaction is widely regarded as a promising technique for improving the efficiency and economics of CO2 utilization processes. Moreover, it is also considered as a pathway towards e-fuels. Cu-oxide catalysts are widely explored for low-temperature RWGS reactions; nevertheless, they tend to deactivate significantly under applied reaction conditions due to the agglomeration of copper particles at elevated temperatures. Herein, we have synthesized homogeneously distributed Cu metallic nanoparticles supported on Mo2C for the RWGS reaction by a unique approach of in situ carburization of metal-organic frameworks (MOFs) using a Cu-based MOF i.e. HKUST-1 encapsulating molybdenum-based polyoxometalates. The newly derived Na-Cu-Mo2C nanocomposite catalyst system exhibits excellent catalytic performance with a CO production rate of 3230.0 mmol gcat-1 h-1 with 100% CO selectivity. Even after 250 h of a stability test, the catalyst remained active with more than 80% of its initial activity.

Quantifying Ultrafast Energy Transfer from Plasmonic Hot Carriers for Pulsed Photocatalysis on Nanostructures.

Photocatalysis with plasmonic nanostructures has lately emerged as a transformative paradigm to drive and alter chemical reactions using light. At the surface of metallic nanoparticles, photoexcitation results in strong near fields, short-lived high-energy "hot" carriers, and light-induced heating, thus creating a local environment where reactions can occur with enhanced efficiencies. In this context, it is critical to understand how to manipulate the nonequilibrium processes triggered by light, as their ultrafast (femto- to picoseconds) relaxation dynamics compete with the process of energy transfer toward the reactants. Accurate predictions of the plasmon photocatalytic activity can lead to optimized nanophotonic architectures with enhanced selectivity and rates, operating beyond the intrinsic limitations of the steady state. Here, we report on an original modeling approach to quantify, with space, time, and energy resolution, the ultrafast energy exchange from plasmonic hot carriers (HCs) to molecular systems adsorbed on the metal nanoparticle surface while consistently accounting for photothermal bond activation. Our analysis, illustrated for a few typical cases, reveals that the most energetic nonequilibrium carriers (i.e., with energies well far from the Fermi level) may introduce a wavelength-dependence of the reaction rates, and it elucidates on the role of the carriers closer to the Fermi energy and the photothermally heated lattice, suggesting ways to enhance and optimize each contribution. We show that the overall reaction rates can benefit strongly from using pulsed illumination with the optimal pulse width determined by the properties of the system. Taken together, these results contribute to the rational design of nanoreactors for pulsed catalysis, which calls for predictive modeling of the ultrafast HC-hot adsorbate energy transfer.