Robert M. Garcia

Donor-acceptor biomorphs from the ionic self-assembly of porphyrins.

Microscale four-leaf clover-shaped structures are formed by self-assembly of anionic and cationic porphyrins. Depending on the metal complexed in the porphyrin macrocycle (Zn or Sn), the porphyrin cores are either electron donors or electron acceptors. All four combinations of these two metals in cationic tetra(N-ethanol-4-pyridinium)porphyrin and anionic tetra(sulfonatophenyl)porphyrin result in related cloverlike structures with similar crystalline packing indicated by X-ray diffraction patterns. The clover morphology transforms as the ionic strength and temperature of the self-assembly reaction are increased, but the structures maintain 4-fold symmetry. The ability to alter the electronic and photophysical properties of these solids (e.g., by altering the metals in the porphyrins) and to vary cooperative interactions between the porphyrin subunits raises the possibility of producing binary solids with tunable functionality. For example, we show that the clovers derived from anionic Zn porphyrins (electron donors) and cationic Sn porphyrins (electron acceptors) are photoconductors, but when the metals are reversed in the two porphyrins, the resulting clovers are insulators.

Synthesis of Platinum Nanowheels Using a Bicellar Template

Disk-like surfactant bicelles provide a unique meso-structured reaction environment for templating the wet-chemical reduction of platinum(II) salt by ascorbic acid to produce platinum nanowheels. The Pt wheels are 496 +/-55 nm in diameter and possess thickened centers and radial dendritic nanosheets (about 2-nm in thickness) culminating in flared dendritic rims. The structural features of the platinum wheels arise from confined growth of platinum within the bilayer that is also limited at edges of the bicelles. The size of CTAB/FC7 bicelles is observed to evolve with the addition of Pt(II) complex and ascorbic acid. Synthetic control is demonstrated by varying the reaction parameters including metal salt concentration, temperature, and total surfactant concentration. This study opens up opportunities for the use of other inhomogeneous soft templates for synthesizing metals, metal alloys, and possibly semiconductors with complex nanostructures.

One-step synthesis of carbon-supported foam-like platinum with enhanced activity and durability

Carbon black nanoparticles localized in-between liposomal bi-layers provide a unique reaction environment that permits one-step synthesis of carbon-supported foam-like platinum (Pt foam/C) in aqueous solution under ambient conditions. The obtained Pt foam/C was readily purified by simple washing with water and chloroform at room temperature. Unlike commercial Pt/C composed of quasi-spherical nanoparticles, Pt foam/C consists of convoluted dendritic nanosheets. Interestingly, Pt foam/C demonstrated both improved durability and activity toward oxygen reduction reaction (ORR). The improved durability is because of the formation of metastable nano-holes among dendritic branches of Pt foam/C under ripening, preserving the surface area. The activity enhancement of Pt foam/C can be attributed to predominantly exposed Pt {1,1,0} planes that possess the highest ORR activity among all low-indexed Pt crystalline planes. Nano-scale Pt primarily enclosed by {1,1,0} planes has not been reported previously.

LDRD final report on synthesis of shape-and size-controlled platinum and platinum alloy nanostructures on carbon with improved durability.

This project is aimed to gain added durability by supporting ripening-resistant dendritic platinum and/or platinum-based alloy nanostructures on carbon. We have developed a new synthetic approach suitable for directly supporting dendritic nanostructures on VXC-72 carbon black (CB), single-walled carbon nanotubes (SWCNTs), and multi-walled carbon nanotubes (MWCNTs). The key of the synthesis is to creating a unique supporting/confining reaction environment by incorporating carbon within lipid bilayer relying on a hydrophobic-hydrophobic interaction. In order to realize size uniformity control over the supported dendritic nanostructures, a fast photocatalytic seeding method based on tin(IV) porphyrins (SnP) developed at Sandia was applied to the synthesis by using SnP-containing liposomes under tungsten light irradiation. For concept approval, one created dendritic platinum nanostructure supported on CB was fabricated into membrane electrode assemblies (MEAs) for durability examination via potential cycling. It appears that carbon supporting is essentially beneficial to an enhanced durability according to our preliminary results.