Bimetallic nanoparticles are of immense scientific and technological interest given the synergistic properties observed when two different metallic species are mixed at the nanoscale. This is particularly prevalent in catalysis, where bimetallic nanoparticles often exhibit improved catalytic activity and durability over their monometallic counterparts. Yet despite intense research efforts, little is understood regarding how to optimize bimetallic surface composition and structure synthetically using rational design principles. Recently, it has been demonstrated that peptide-enabled routes for nanoparticle synthesis result in materials with sequence-dependent catalytic properties, providing an opportunity for rational design through sequence manipulation. In this study, bimetallic PdAu nanoparticles are synthesized with a small set of peptides containing known Pd and Au binding motifs. The resulting nanoparticles were extensively characterized using high-resolution scanning transmission electron microscopy, X-ray absorption spectroscopy, and high-energy X-ray diffraction coupled to atomic pair distribution function analysis. Structural information obtained from synchrotron radiation methods was then used to generate model nanoparticle configurations using reverse Monte Carlo simulations, which illustrate sequence dependence in both surface structure and surface composition. Replica exchange with solute tempering molecular dynamics simulations were also used to predict the modes of peptide binding on monometallic surfaces, indicating that different sequences bind to the metal interfaces via different mechanisms. As a testbed reaction, electrocatalytic methanol oxidation experiments were performed, wherein differences in catalytic activity are clearly observed in materials with identical bimetallic composition. Taken together, this study indicates that peptides could be used to arrive at bimetallic surfaces with enhanced catalytic properties, which could be leveraged for rational bimetallic nanoparticle design using peptide-enabled approaches.
Bibliographical noteFunding Information:
The use of beamlines 11-ID-C and 12-BM of the Advanced Photon Source is supported by the U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Z.E.H. thanks the Royal Society of Chemistry (RSC) for travel funds made available under the Journal Grants for International Authors scheme to assist in facilitating the reported research. This research was undertaken with the assistance of resources from the National Computational Infrastructure (NCI), which is supported by the Australian Government. T.R.W. thanks veski for an Innovation Fellowship. This work was partially supported by the Air Force Office for Scientific Research (T.R.W., Grant No. FA9550-12- 620 1-0226). S.P.E. and E.B.C. gratefully acknowledge financial support from the Army Research Office through a MURI award, W911NF-10-1-0520, and the central analytical facilities supported by the NSF-Sponsored MRSEC at UMass Amherst. We would like to thank Prof. Brian Gorman of the Colorado School of Mines with assistance with EDS mapping experiments.
- X-ray absorption spectroscopy
- atomic pair distribution function analysis
- bimetallic nanoparticles
- peptide-enabled nanoparticles