There is a growing interest in controlling the synthesis of colloidal metal nanocrystals and thus tailoring their properties toward various applications. In this context, choosing an appropriate ...combination of reagents (e.g., salt precursor, reductant, capping agent, and stabilizer) plays a pivotal role in enabling the synthesis of metal nanocrystals with diversified sizes, shapes, and structures. Here we present a comprehensive review that highlights one of the key reagents for the synthesis of metal nanocrystals via chemical reduction: the reductants. We start with a brief introduction to the compounds commonly employed as reductants in the colloidal synthesis of metal nanocrystals by showing their oxidation half‐reactions and the corresponding oxidation potentials. Then we offer specific examples pertaining to the controlled synthesis of metal nanocrystals, followed by some fundamental aspects covering the general mechanisms of metal ion reduction based on the Marcus Theory. Afterwards, we present a case‐by‐case discussion on a wide variety of reductants, including their major properties, reduction mechanisms, and additional effects on the final products. We illustrate these aspects by selecting key examples from the literature and paying close attention to the underlying mechanism in each case. At the end, we conclude by summarizing the highlights of the review and providing some perspectives on future directions.
Reductants play a pivotal role in controlling the shapes and surface structures of noble‐metal nanocrystals, which affect both the reaction kinetics and thermodynamics significantly. By choosing an appropriate reductant, one is able to produce various noble metal nanocrystals with a variety of shapes, with typical examples including Pd, Pt, Au, Ag, and Rh.
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Noble-metal nanoparticles have been widely employed in catalysis. As catalytic properties are dependent on their physical/chemical parameters, strategies for their controlled synthesis and the ...understanding of performance relationships have gained attention. In this review, we discuss developments on well-defined noble-metal nanoparticles focusing on relationships between performance and physical/chemical features. We begin with the control over shape, composition, and size. Then, we focus on nanoparticles with hollow interiors, which provide further possibilities for performance optimization. We provide a case-by-case discussion to illustrate how, in addition to the hollow interiors, the control over their composition, size, and surface morphology relate to catalytic performance.
This review discusses the importance of physical/chemical control in metallic NPs for the optimization and understanding of catalytic performances.
Metallic nanoparticles have been extensively studied towards applications in catalysis. Among the several methods for their controlled synthesis, galvanic replacement is particularly attractive as it ...enables the production of bimetallic and hollow nanomaterials displaying ultrathin walls in a single reaction step. This procedure is versatile, but final morphologies are often limited to shapes that represent the hollow analogues of the starting template nanocrystals. For catalytic applications, it is highly desirable to broaden the scope of physicochemical control that can be achieved by this method. This feature article discusses recent strategies developed in our group for the synthesis of hollow bimetallic nanomaterials by galvanic replacement that enable a further level of control over surface morphologies and composition. We begin by briefly explaining the fundamentals of the conventional galvanic replacement reaction between Ag and AuCl
4
−
. This is one of the most characteristic galvanic replacement reactions, and it can be tuned to create a huge variety of nanoparticle morphologies. We will discuss how advanced electron microscopy characterization enables us to uncover surface-segregation behavior as a function of compositions, and relate this to the detected catalytic performance. We will also discuss how galvanic replacement can be extended to trimetallic compositions, leading to improvements in catalytic activities compared to mono or bimetallic counterparts. Furthermore, we will show how surface morphology, size, and anisotropic growth can be controlled by tuning the temperature during the synthesis and by combining galvanic replacement reaction with co-reduction. Finally, we will demonstrate how these approaches are promising for large-scale synthesis of controlled hollow nanostructures and their incorporation into supports to produce catalysts at the gram-scale. We believe the developments described herein shed important insights and may inspire the development of sophisticated and controlled nanomaterials at relatively larger scales for catalytic applications.
Recent developments to achieve further physicochemical control in metallic nanomaterials by galvanic replacement are discussed towards applications in catalysis.
In the face of increasing bacterial resistance to antibiotics currently in use, the search for new antimicrobial agents has received a boost in recent years, with natural products playing an ...important role in this field. In fact, several methods have been proposed to investigate the antibacterial activities of natural products. However, given that the ultimate aim is future therapeutic use as novel drugs, it is extremely necessary to elucidate their modes of action, stating the molecular effects in detail, and identifying their targets in the bacterial cell. This review analyzes the application of "omics technologies" to understand the antibacterial mechanisms of bioactive natural products, to stimulate research interest in this area and promote scientific collaborations. Some studies have been specifically highlighted herein by examining their procedures and results (targeted proteins and metabolic pathways). These approaches have the potential to provide new insights into our comprehension of antimicrobial resistance/susceptibility, creating new perspectives for the struggle against bacteria, and leading to the development of novel products in the future.
To develop evidence-based recommendations for the management of fibromyalgia syndrome.
A multidisciplinary task force was formed representing 11 European countries. The design of the study, including ...search strategy, participants, interventions, outcome measures, data collection and analytical method, was defined at the outset. A systematic review was undertaken with the keywords "fibromyalgia", "treatment or management" and "trial". Studies were excluded if they did not utilise the American College of Rheumatology classification criteria, were not clinical trials, or included patients with chronic fatigue syndrome or myalgic encephalomyelitis. Primary outcome measures were change in pain assessed by visual analogue scale and fibromyalgia impact questionnaire. The quality of the studies was categorised based on randomisation, blinding and allocation concealment. Only the highest quality studies were used to base recommendations on. When there was insufficient evidence from the literature, a Delphi process was used to provide basis for recommendation.
146 studies were eligible for the review. 39 pharmacological intervention studies and 59 non-pharmacological were included in the final recommendation summary tables once those of a lower quality or with insufficient data were separated. The categories of treatment identified were antidepressants, analgesics, and "other pharmacological" and exercise, cognitive behavioural therapy, education, dietary interventions and "other non-pharmacological". In many studies sample size was small and the quality of the study was insufficient for strong recommendations to be made.
Nine recommendations for the management of fibromyalgia syndrome were developed using a systematic review and expert consensus.
The study focuses on the equilibrium of dynamic biosorption in single and binary systems containing Cu(II) and Ni(II) ions using Sargassum filipendula (a marine alga). The experiments were performed ...in fixed-bed columns with both single-component and bi-component metal solutions (using different molar concentrations). Experimental data were fitted with different equilibrium models such as Langmuir, Langmuir with inhibition, Jain and Snowyink and Langmuir-Freundlich equations. The biosorption of pure metal ions in solution presented adequate capacities both for Cu(II) and Ni(II). In binary solutions the preferential sorption of Cu(II) over Ni(II) was demonstrated by the displacement of Ni(II) (marked overshoot on the breakthrough curves).
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Nanorattles, comprised of a nanosphere inside a nanoshell, were employed as the next generation of plasmonic catalysts for oxidations promoted by activated O2. After investigating how the presence of ...a nanosphere inside a nanoshell affected the electric‐field enhancements in the nanorattle relative to a nanoshell and a nanosphere, the SPR‐mediated oxidation of p‐aminothiophenol (PATP) functionalized at their surface was investigated to benchmark how these different electric‐field intensities affected the performances of Au@AgAu nanorattles, AgAu nanoshells and Au nanoparticles having similar sizes. The high performance of the nanorattles enabled the visible‐light driven synthesis of azobenzene from aniline under ambient conditions. As the nanorattles allow the formation of electromagnetic hot spots without relying on the uncontrolled aggregation of nanostructures, it enables their application as catalysts in liquid phase under mild conditions using visible light as the main energy input.
Nanorattles: By taking advantage of the plasmon hybridization concept in Au@AgAu nanorattles, improved performances towards the surface plasmon resonance‐mediated oxidation of amines were achieved. As the nanorattle morphology makes possible the formation of electromagnetic hot spots, these materials are attractive next‐generation plasmonic catalysts for applications in liquid‐phase transformations under mild conditions.
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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.
Recent efforts on the use of controlled metal nanoparticles to establish structure-performance relationships in plasmonic catalysis are discussed.
Adhesive bonding has become more efficient in the last few decades due to the adhesives developments, granting higher strength and ductility. On the other hand, natural fibre composites have recently ...gained interest due to the low cost and density. It is therefore essential to predict the fracture behavior of joints between these materials, to assess the feasibility of joining or repairing with adhesives. In this work, the tensile fracture toughness (Gnc) of adhesive joints between natural fibre composites is studied, by bonding with a ductile adhesive and co-curing. Conventional methods to obtain Gnc are used for the co-cured specimens, while for the adhesive within the bonded joint, the J-integral is considered. For the J-integral calculation, an optical measurement method is developed for the evaluation of the crack tip opening and adherends rotation at the crack tip during the test, supported by a Matlab sub-routine for the automated extraction of these quantities. As output of this work, an optical method that allows an easier and quicker extraction of the parameters to obtain Gnc than the available methods is proposed (by the J-integral technique), and the fracture behaviour in tension of bonded and co-cured joints in jute-reinforced natural fibre composites is also provided for the subsequent strength prediction. Additionally, for the adhesively-bonded joints, the tensile cohesive law of the adhesive is derived by the direct method.
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In this paper the kinetics and dynamics of nickel adsorption on calcined Bofe bentonite clay were studied. The clay was characterized through EDX, surface area (BET) and XRD analysis. The influence ...of parameters (pH, amount of adsorbent, adsorbate concentration and temperature) was investigated. Kinetic models were evaluated in order to identify potential adsorption process mechanisms. The Langmuir and Freundlich models were utilized for the analysis of adsorption equilibrium. Thermodynamic parameters were assessed as a function of the process temperature. The kinetics data were better represented by the second-order model. The process was found to be strongly influenced by the factors studied. The Bofe clay removed nickel with maximum adsorption capacity of 1.91
mg metal/g of clay (20
°C; pH 5.3) and that the thermodynamic data indicated that the adsorption reaction is spontaneous and of an exothermal nature. The Langmuir model provided the best fit for sorption isotherms.
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