An experimental perspective on nanoparticle electrochemistry.

While model studies with small nanoparticles offer a bridge between applied experiments and theoretical calculations, the intricacies of working with well-defined nanoparticles in electrochemistry pose challenges for experimental researchers. This perspective dives into nanoparticle electrochemistry, provides experimental insights to uncover their intrinsic catalytic activity and draws conclusions about the effects of altering their size, composition, or loading. Our goal is to help uncover unexpected contamination sources and establish a robust experimental methodology, which eliminates external parameters that can overshadow the intrinsic activity of the nanoparticles. Additionally, we explore the experimental difficulties that can be encountered, such as stability issues, and offer strategies to mitigate their impact. From support preparation to electrocatalytic tests, we guide the reader through the entire process, shedding light on potential challenges and crucial experimental details when working with these complex systems.

CuNi Nanoalloys with Tunable Composition and Oxygen Defects for the Enhancement of the Oxygen Evolution Reaction.

Colloidal synthesis is an excellent tool for the study of cooperative effects in nanoalloys. In this work, bimetallic CuNi nanoparticles of defined size and composition are fully characterized and tested for the oxygen evolution reaction. Copper addition to nickel leads to modifications in the structural and electronic properties, showing a higher concentration of surface oxygen defects and formation of active Ni3+ sites under reaction conditions. The ratio OV /OL between oxygen vacancies and lattice oxygen shows a clear correlation with the overpotential, being an excellent descriptor of the electrocatalytic activity. This is attributed to modifications in the crystalline structure, leading to lattice strain and grain size effects. Bimetallic Cu50 Ni50 NP showed the lowest overpotential (318 mV vs RHE), low Tafel slope (63.9 mV dec-1 ), and excellent stability. This work unravels the relative concentration between oxygen defects and lattice oxygen (OV /OL ) as an excellent descriptor of the catalytic activity of bimetallic precatalysts.

Rational design of tandem catalysts using a core-shell structure approach.

A facile and rational approach to synthesize bimetallic heterogeneous tandem catalysts is presented. Using core-shell structures, it is possible to create spatially controlled ensembles of different nanoparticles and investigate coupled chemocatalytic reactions. The CO2 hydrogenation to methane and light olefins was tested, achieving a tandem process successfully.