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Catalysis is central to a more sustainable future and a circular economy. If the energy required to drive catalytic processes could be harvested directly from sunlight, the possibility of replacing contemporary processes based on terrestrial fuels by the conversion of light into chemical energy could become a step closer to reality. Plasmonic catalysis is currently at the forefront of photocatalysis, enabling one to overcome the limitations of "classical" wide bandgap semiconductors for solar-driven chemistry. Plasmonic catalysis enables the acceleration and control of a variety of molecular transformations due to the localized surface plasmon resonance (LSPR) excitation. Studies in this area have often focused on the fundamental understanding of plasmonic catalysis and the demonstration of plasmonic catalytic activities towards different reactions. In this feature article, we discuss recent contributions from our group in this field by employing plasmonic nanoparticles (NPs) with controllable features as model systems to gain insights into structure-performance relationships in plasmonic catalysis. We start by discussing the effect of size, shape, and composition in plasmonic NPs over their activities towards LSPR-mediated molecular transformations. Then, we focus on the effect of metal support interactions over activities, reaction selectivity, and reaction pathways. Next, we shift to the control over the structure in hollow NPs and nanorattles. Inspired by the findings from these model systems, we demonstrate a design-driven strategy for the development of plasmonic catalysts based on plasmonic-catalytic multicomponent NPs for two types of molecular transformations: the selective hydrogenation of phenylacetylene and the oxygen evolution reaction. Finally, future directions, challenges, and perspectives in the field of plasmonic catalysis with designer NPs are discussed. We believe that the examples and concepts presented herein may inspire work and progress in plasmonic catalysis encompassing the design of plasmonic multicomponent materials, new strategies to control reaction selectivity, and the unraveling of stability and reaction mechanisms.

RESUMO

A photoelectrochemical biosensing strategy for the highly sensitive detection of the flavonoid rutin was developed by synergizing the photoelectrocatalytic properties of hematite (α-Fe2O3) decorated with palladium nanoparticles (PdNPs) and the biocatalysis towards laccase-based reactions. The integration of α-Fe2O3.PdNPs with a polyphenol oxidase as a biorecognition element yields a novel biosensing platform. Under visible light irradiation, the photoactive biocomposite can generate a stable photocurrent, which was found to be directly dependent upon the concentration of rutin. Under the optimal experimental conditions, the cathodic photocurrent, measured at 0.33 V vs. Ag/AgCl, from the square-wave voltammograms presented a linear dependence on the rutin concentration within the range of 0.008-30.0 × 10-8 mol L-1 (sensitivity: 1.7 µA·(× 10-8 M-1)·cm-2), with an experimental detection limit (S/N = 3) of 8.4 × 10-11 mol L-1. The proposed biosensor device presented good selectivity towards rutin in the presence of various organic compounds and inorganic ions, demonstrating the potential application of this biosensing platform in complex matrices. This bioanalytical device also exhibited excellent operational and analytical properties, such as intra-day (standard deviation, SD = 0.21%) and inter-day (SD = 1.30%) repeatability, and long storage stability (SD = 2.80% over 30 days).Graphical abstract.

Assuntos

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Solar-to-chemical conversion via photocatalysis is of paramount importance for a sustainable future. Thus, investigating the synergistic effects promoted by light in photocatalytic reactions is crucial. The tandem oxidative coupling of alcohols and amines is an attractive route to synthesize imines. Here, we unravel the performance and underlying reaction pathway in the visible-light-driven tandem oxidative coupling of benzyl alcohol and aniline employing Au/CeO2 nanorods as catalysts. We propose an alternative reaction pathway for this transformation that leads to improved efficiencies relative to individual CeO2 nanorods, in which the localized surface plasmon resonance (LSPR) excitation in Au nanoparticles (NPs) plays an important role. Our data suggests a synergism between the hot electrons and holes generated from the LSPR excitation in Au NPs. While the oxygen vacancies in CeO2 nanorods trap the hot electrons and facilitate their transfer to adsorbed O2 at surface vacancy sites, the hot holes in the Au NPs facilitate the α-H abstraction from the adsorbed benzyl alcohol, evolving into benzaldehyde, which then couples with aniline in the next step to yield the corresponding imine. Finally, cerium-coordinated superoxide species abstract hydrogen from the Au surface, regenerating the catalyst surface.

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Current time-resolved in situ approaches limit the scope of mechanochemical investigations possible. Here we develop a new, general approach to simultaneously follow the evolution of bulk atomic and electronic structure during a mechanochemical synthesis. This is achieved by coupling two complementary synchrotron-based X-ray methods: X-ray absorption spectroscopy (XAS) and X-ray diffraction. We apply this method to investigate the bottom-up mechanosynthesis of technologically important Au micro and nanoparticles in the presence of three different reducing agents, hydroquinone, sodium citrate, and NaBH4. Moreover, we show how XAS offers new insight into the early stage generation of growth species (e.g. monomers and clusters), which lead to the subsequent formation of nanoparticles. These processes are beyond the detection capabilities of diffraction methods. This combined X-ray approach paves the way to new directions in mechanochemical research of advanced electronic materials.

RESUMO

The interaction of metallic nanoparticles with light excites a local surface plasmon resonance (LSPR). This phenomenon enables the transfer of hot electrons to substrates that release Reactive Oxygen Species (ROS). In this context, the present study aimed at enhancing the antibacterial effect of citrate-covered silver nanoparticles (AgNPs) by LSPR excitation with visible LED. AgNPs possess excellent antimicrobial properties against Pseudomonas aeruginosa, one of the most refractory organisms to antibiotic treatment. The Minimum Inhibitory Concentration (MIC) of the AgNPs was 10 µg/ml under dark conditions and 5 µg/ml under light conditions. The combination of light and AgNPs led to 100% cell death after 60 min. Flow cytometry quantification showed that bacteria treated with LSPR-stimulated AgNPs displayed 4.8 times more ROS. This significant increase in ROS possibly accounts for most of the antimicrobial effect of the AgNPs. In addition, light exposition caused a small release of silver ions (0.4%) suggesting that silver ions may play a secondary role in P. aeruginosa death. Overall, the results presented here show that LSPR stimulation of AgNPs by visible light enhances the antimicrobial activity of silver nanoparticles and can be an alternative for the treatment of topic infections caused by antibiotic-resistant bacteria such as P. aeruginosa.

Assuntos

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We develop herein plasmonic-catalytic Au-IrO2 nanostructures with a morphology optimized for efficient light harvesting and catalytic surface area; the nanoparticles have a nanoflower morphology, with closely spaced Au branches all partially covered by an ultrathin (1 nm) IrO2 shell. This nanoparticle architecture optimizes optical features due to the interactions of closely spaced plasmonic branches forming electromagnetic hot spots, and the ultra-thin IrO2 layer maximizes efficient use of this expensive catalyst. This concept was evaluated towards the enhancement of the electrocatalytic performances towards the oxygen evolution reaction (OER) as a model transformation. The OER can play a central role in meeting future energy demands but the performance of conventional electrocatalysts in this reaction is limited by the sluggish OER kinetics. We demonstrate an improvement of the OER performance for one of the most active OER catalysts, IrO2, by harvesting plasmonic effects from visible light illumination in multimetallic nanoparticles. We find that the OER activity for the Au-IrO2 nanoflowers can be improved under LSPR excitation, matching best properties reported in the literature. Our simulations and electrocatalytic data demonstrate that the enhancement in OER activities can be attributed to an electronic interaction between Au and IrO2 and to the activation of Ir-O bonds by LSPR excited hot holes, leading to a change in the reaction mechanism (rate-determinant step) under visible light illumination.

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A mechano-colloidal approach was developed to produce Au nanotadpoles. It comprises the generation of seeds by ball-milling from a solid mixture containing a precursor, reductant, and capping agent, followed by the dispersion of this mixture in water leading to seeded-growth to generate the target nanoparticle morphology.

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In this study, (1→3)(1→6)-ß-D-glucan (botryosphaeran) from Botryosphaeria rhodina MAMB-05 was used, for the first time, to immobilize laccase on a carbon black paste electrode modified with gold nanoparticles. The physicochemical characterization of the proposed laccase-biosensor was performed using transmission electron microscopy and electrochemical impedance spectroscopy. The performance of this novel bio-device was evaluated by choosing hydroquinone as a typical model of a phenolic compound. For hydroquinone determination, experimental variables such as enzyme concentration, pH and operational parameters of the electroanalytical technique were optimized. From square-wave voltammograms, a linear dependence between the cathodic current peak and the hydroquinone concentration was observed within the range 2.00-56.5µmolL-1, with a theoretical detection limit of 0.474µmolL-1. The proposed method was successfully applied to determine hydroquinone in dermatological cream, and samples from biological and environmental niches. The proposed biosensor device presented good selectivity in the presence of uric acid, various inorganic ions, as well as other phenolic compounds, demonstrating the potential application of this biosensing platform in complex matrices. Operational and analytical stability of the laccase biosensor were evaluated, and demonstrated good intra-day (SD=0.3%) and inter-day (SD=3.4%) repeatability and long storage stability (SD=4.9%).

Assuntos

RESUMO

The localized surface plasmon resonance (LSPR) excitation in plasmonic nanoparticles has been used to accelerate several catalytic transformations under visible-light irradiation. In order to fully harness the potential of plasmonic catalysis, multimetallic nanoparticles containing a plasmonic and a catalytic component, where LSPR-excited energetic charge carriers and the intrinsic catalytic active sites work synergistically, have raised increased attention. Despite several exciting studies observing rate enhancements, controlling reaction selectivity remains very challenging. Here, by employing multimetallic nanoparticles combining Au, Ag, and Pt in an Au@Ag@Pt core-shell and an Au@AgPt nanorattle architectures, we demonstrate that reaction selectivity of a sequential reaction can be controlled under visible light illumination. The control of the reaction selectivity in plasmonic catalysis was demonstrated for the hydrogenation of phenylacetylene as a model transformation. We have found that the localized interaction between the triple bond in phenylacetylene and the Pt nanoparticle surface enables selective hydrogenation of the triple bond (relative to the double bond in styrene) under visible light illumination. Atomistic calculations show that the enhanced selectivity toward the partial hydrogenation product is driven by distinct adsorption configurations and charge delocalization of the reactant and the reaction intermediate at the catalyst surface. We believe these results will contribute to the use of plasmonic catalysis to drive and control a wealth of selective molecular transformations under ecofriendly conditions and visible light illumination.

RESUMO

The use of sunlight to drive chemical reactions via photocatalysis is of paramount importance towards a sustainable future. Among several photocatalysts, earth-abundant polymeric carbon nitride (PCN, often wrongly named g-C3N4) has emerged as an attractive candidate due to its ability to absorb light efficiently in the visible and near-infrared ranges, chemical stability, non-toxicity, straightforward synthesis, and versatility as a platform for constructing hybrid materials. Especially, hybrids with metal nanoparticles offer the unique possibility of combining the catalytic, electronic, and optical properties of metal nanoparticles with PCN. Here, we provide a comprehensive overview of PCN materials and their hybrids, emphasizing heterostructures with metal nanoparticles. We focus on recent advances encompassing synthetic strategies, design principles, photocatalytic applications, and charge-transfer mechanisms. We also discuss how the localized surface plasmon resonance (LSPR) effect of some noble metals NPs (e.g. Au, Ag, and Cu), bimetallic compositions, and even non-noble metals NPs (e.g., Bi) synergistically contribute with PCN in light-driven transformations. Finally, we provide a perspective on the field, in which the understanding of the enhancement mechanisms combined with truly controlled synthesis can act as a powerful tool to the establishment of the design principles needed to take the field of photocatalysis with PCN to a new level, where the desired properties and performances can be planned in advance, and the target material synthesized accordingly.