Converting nanocrystalline metals into alloys and intermetallic compounds for applications in catalysis

Abstract
Multi-metal nanoparticles, particularly alloys and intermetallic compounds, are useful catalysts for a variety of chemical transformations. Supported intermetallic nanoparticle catalysts are usually prepared by depositing precursors onto a support followed by high-temperature annealing, which is necessary to generate the intermetallic compound but causes sintering and minimizes surface area. Here we show that solution chemistry methods for converting metal nanoparticles into intermetallic compounds are applicable to supported nanoparticle catalyst systems. Unsupported nanocrystalline Pt can be converted to nanocrystalline PtSn, PtPb, PtBi, and FePt3 by reaction with appropriate metal salt solutions under reducing conditions. Similar reactions convert Al2O3, CeO2, and carbon-supported Pt nanoparticles into PtSn, PtPb, PtSb, Pt3Sn, and Cu3Pt. These reactions generate supported alloy and intermetallic nanoparticles directly in solution without the need for high temperature annealing or additional surface stabilizers. These supported intermetallic nanoparticles are catalytically active for chemical transformations such as formic acid oxidation (PtPb/Vulcan) and CO oxidation (Pt3Sn/graphite). Notably, PtPb/Vulcan XC-72 was found to electrocatalytically oxidize formic acid at a lower onset potential (0.1 V) than commercial PtRu/Vulcan XC-72 (0.4 V).