Pd-Based Nanoalloys for Electrochemical Reactions

Dear Colleagues,

Currently, the design of highly active and stable catalysts using Pd and Pd-based nanomaterials has become an area of intense interest. Pd is well known for its high affinity for hydrogen, which facilitates the broad use of Pd nanomaterials as primary catalysts in a wide variety of applications, particularly, organic coupling synthesis, hydrogen detection, purification, and storage.

The abundance of Pd within the crust of the earth is three-fold higher than that of Pt, and, through the use of diverse synthesis techniques, Pd-based nanomaterials have the potential to provide superior and cost-effective solutions to meet the requirements of present and evolving electrochemical applications, specifically, for the development of a hydrogen economy.

As a face-centered cubic (fcc) metal, Pd has the capacity to form a variety of geometrical shapes. These myriad morphologies may be achieved through the manipulation of either the thermodynamics or the kinetics involved in crystal growth. Morphological aspects offer greater versatility than dimensions and other parameters when tuning the catalytic properties of nanocrystals, because atoms that are resident in different facets possess diverse activity. It is surmised that the catalytic activity and selectivity of small nanoparticles is largely dependent on the structure and size effects at the nanoscale. Distinct nanoparticle–substrate interactions, which may be a combination of electronic (e.g., nanoparticle/support charge transfer) and poststructural (e.g., strain effects at the nanoparticle/support interface) effects, may facilitate the understanding of shape and size effects. The fabrication of nanostructured Pd materials with controllable morphologies and dimensions has been achieved by means of physical synthesis techniques (sputtering, ion or electron beam deposition, and laser ablation), hydrothermal methods (that are promising green synthesis techniques), electrodeposition techniques, electroless deposition, microemulsions, and photochemical synthesis. This broad range of techniques allows for morphologies, dimensions, and interparticle distances to be tailored, leading to the desired nanostructures.

Over the past decade, there have been some reports about decreasing the loading amount of Pd in catalysts with enhanced performance by alloying Pd with transition metals and other elements. The main important factors that influence the catalytic activity of these bimetallic and trimetallic nanoalloys are the electronic and geometric effect (using carbon-based stabilizers such as graphene and carbon black) and various other effects, including defects, a synergistic effect, change of the d-band center of palladium, and surface strain. The fields of direct alcohol fuel cells, electrochemical oxidation of formic acid, electrochemical reduction of oxygen, electrochemical reduction of hydrogen peroxide, hydrogen production, purification and storage, electrochemical sensors and biosensors, and electrodegradation of pollutants offer key application opportunities for novel Pd-based nanoalloys developed by new synthesis techniques and presenting unique properties.  

This Special Issue of Nanomaterials will attempt to cover the most recent advances in Pd-based nanoalloys concerning not only their synthesis and characterization but also their activity, functionality, durability, and low cost for electrochemical applications.

Prof. Dr. César Augusto Correia de Sequeira
Guest Editor

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