Materials and structures thereof useful as electrocatalysts

A nanostructured electrode comprising:

• a conductive glassy carbon electrode substrate containing covalently grafted surface functional groups which support binding of multilayers and having an initial layer of positive charge on the surface;
• a platinum nanoparticle stabilized by covalently bonded negatively-charged ligands wherein said platinum nanoparticle is covalently bound to tris-[4-phosphonatophenyl]phosphine ligand;
• and
• a polyelectrolyte.

A nanostructured electrode comprising:

• a conductive glassy carbon electrode substrate;
• a surface functional group covalently grafted to the conductive glassy carbon electrode substrate wherein the surface functional group covalently grafted provides a layer of negative charge;
• a nanoparticle stabilized by covalently bonded ligands bearing a positively-charged peripheral functional group;
• and
• a material capable of binding to said peripheral functional group.

A nanostructured electrode comprising:

• a plurality of catalytic nanoparticles;
• wherein said plurality of catalytic nanoparticles comprise electron conducting metal-containing nanoparticles with surfaces containing covalently bound ligands,
• wherein said ligands bear one or more substituents on the peripheries of said ligands,
• wherein at least one of said substituents is charged,
• wherein the covalently bound ligands and the one or more substituents tune the catalytic properties of the catalytic nanoparticles;
• and
• a bridging material comprising one selected from the group consisting of a polyelectrolyte, a metal ion, and a second nanoparticle having a net charge opposite of the plurality of catalytic nanoparticles;
• wherein the bridging material conducts or transports protons or holes and is deposited on an electrically conductive substrate surface in alternating layers between said catalytic nanoparticles providing a composite film containing both electron conductive and proton conductive component layers arranged in a manner to maximize their interfacial contact area
• while maintaining electrical communication with said electrically conductive substrate and a fuel cell electrolyte solution.