Controlled synthesis of noble metal nanomaterials: motivation, principles, and opportunities in nanocatalysis

ABSTRACT This review describes some principles of the controlled synthesis of metal nanoparticles, focusing on how the fundamental understanding of their synthesis in the solution-phase can be put to tailor size, shape, composition, and architecture. The maneuvering over these parameters not only enable the tuning of properties, but also the maximization and optimization of performances for various applications. Herein, we start with a brief description of metallic nanoparticles, highlighting the motivation for achieving physicochemical control in their synthesis. After that, we turn our attention to some important definitions and classifications as well as their unique properties such as surface and quantum effects. Moreover, we discuss the strategies for the controlled synthesis of metal nanomaterials based on the top-down and bottom-up approaches, focusing our discussion on their formation mechanisms in liquid-phase in terms of both thermodynamic and kinetic control. Finally, we point out the promising applications of controlled nanomaterials in the field of nanocatalysis and plasmon-enhanced catalysis, describing some of the current challenges in these fields

Controlling Selectivity in Plasmonic Catalysis: Switching Reaction Pathway from Hydrogenation to Homocoupling Under Visible-Light Irradiation

Plasmonic catalysis enables the use of light to accelerate molecular transformations. Its application to the control reaction selectivity is highly attractive but remains challenging. Here, we have found that the plasmonic properties in AgPd nanoparticles allowed different reaction pathways for tunable product formation under visible-light irradiation. By employing the hydrogenation of phenylacetylene as a model transformation, we demonstrate that visible-light irradiation can be employed to steer the reaction pathway from hydrogenation to homocoupling. Our data showed that the decrease in the concentration of H species at the surface due to plasmon-enhanced H2 desorption led to the control in selectivity. These results provide important insights into the understanding of reaction selectivity with light, paving the way for the application of plasmonic catalysis to the synthesis of 1,3-diynes, and bringing the vision of light-driven transformations with target selectivity one step closer to reality.</p

Cu2O spheres as an efficient source of catalytic Cu(I) species for performing azide-alkyne click reactions

We report herein the high yield synthesis of Cu2O spheres displaying well-defined shapes and monodisperse sizes that could be employed as the source of highly catalytic active Cu(I) species towards click reactions between several of alkynes and azides to produce a variety of 1,2,3-triazoles under ligand-free and ambient conditions (in an open reactor). The utilization of Cu2O spheres enabled superior performance as compared to a conventional protocol in which CuSO4 is employed in combination with sodium ascorbate as the catalyst system. In addition, the compounds were obtained in synthetically useful yields, and seven of them have not been previously reported. We believe the results reported herein shed new insights into the optimization of activity and versatility of click reactions towards the synthesis of target molecules in environmentally friendly conditions

Combining active phase and support optimization in MnO2-Au nanoflowers: Enabling high activities towards green oxidations

International audienc

STEM-EDX tomography of bimetallic nanoparticles:A methodological investigation

AbstractThis paper presents an investigation of the limitations and optimisation of energy dispersive X-ray (EDX) tomography within the scanning transmission electron microscope, focussing on application of the technique to characterising the 3D elemental distribution of bimetallic AgAu nanoparticles. The detector collection efficiency when using a standard tomography holder is characterised using a tomographic data set from a single nanoparticle and compared to a standard low background double tilt holder. Optical depth profiling is used to investigate the angles and origin of detector shadowing as a function of specimen field of view. A novel time-varied acquisition scheme is described to compensate for variations in the intensity of spectrum images at each sample tilt. Finally, the ability of EDX spectrum images to satisfy the projection requirement for nanoparticle samples is discussed, with consideration of the effect of absorption and shadowing variations

Resistência do solo à penetração, após o tráfego com dois tipos de pneus utilizando-se um equipamento para ensaio dinâmico Soil penetration resistance after the traffic with two types of tyres using the dynamic test equipment

Com este trabalho objetivou-se, principalmente, avaliar a resistência do solo à penetração, em função do tipo de pneu (diagonal e radial) e da carga vertical, utilizando-se um equipamento de ensaio de pneu agrícola individual, e verificar os efeitos nas camadas do solo pela passagem do pneu. O equipamento utilizado foi projetado para ser acoplado na traseira do trator e acionado pela tomada de potência afim de realizar ensaios de pneus em condições de campo, sendo ainda, constituído, de uma caixa de transmissão mecânica de trator e instrumentos eletrônicos de medição. Este trabalho foi desenvolvido no Núcleo de Engenharia Rural da Faculdade de Ciências Agronômicas (FCA/UNESP) em Botucatu. Os dados obtidos no experimento foram analisados considerando-se o delineamento experimental em blocos, no esquema de parcelas subdivididas, tendo na parcela os pneus (radial e diagonal) e na subparcelas as cargas (10.000, 13.000, 16.000 e 19.000 N) com cinco repetições. O pneu radial mostrou vantagem em relação ao diagonal, por apresentar menores valores de índice de cone. As cargas mais elevadas provocaram maiores valores de índice de cone e seus incrementos, nas camadas de 0 a 10 e de 10 a 20 cm.<br>The main objective of this research was to evaluate the soil cone index results as a function of tyre type (radial and bias tyres) and tyre load using a single wheel testing equipment and verifying the effect on the layers after tyre traffic. This equipment was projected for linking at the rear of a tractor and was activated by the power with the purpose of testing individual tyre under field conditions and constituted of a mechanical transmission box and electronic instruments of measurement. This study was conducted at the Agricultural Tyre Testing Center - NEMPA of Rural Engineering Department, Faculty of Agronomic Sciences, UNESP, Botucatu, SP. The data obtained were analyzed considering a random block experimental design in split plot with tyre in the main plot (radial and bias tyres) and tyre load (10.000 N, 13.000 N, 16.000 N and 19.000 N) in the split plots with five repetitions. The radial tyre showed advantage in relation to bias tyre showing small cone index values. The highest loads provoked largest cone index values and its increments in the layers of 0 to 10 cm and 10 to 20 cm