| AVS 64th International Symposium & Exhibition | |
| Fundamental Discoveries in Heterogeneous Catalysis Focus Topic | Wednesday Sessions |
| Session HC+NS+SS-WeM |
| Session: | Nanoscale Surface Structures in Heterogeneously-Catalyzed Reactions |
| Presenter: | E. Charles Sykes, Tufts University |
| Correspondent: | Click to Email |
Catalytic hydrogenations are critical steps in many industries including agricultural chemicals, foods and pharmaceuticals. In the petroleum refining, for instance, catalytic hydrogenations are performed to produce light and hydrogen rich products like gasoline. Typical heterogeneous hydrogenation catalysts involve nanoparticles composed of expensive noble metals or alloys based on platinum, palladium, rhodium, and ruthenium. We demonstrated for the first time how single palladium atoms can convert the otherwise catalytically inert surface of an inexpensive metal into an ultraselective catalyst. High-resolution imaging allowed us to characterize the active sites in single atom alloy surfaces, and temperature programmed reaction spectroscopy to probe the chemistry. The mechanism involves facile dissociation of hydrogen at individual palladium atoms followed by spillover onto the copper surface, where ultraselective catalysis occurs by virtue of weak binding. The reaction selectivity is in fact much higher than that measured on palladium alone, illustrating the system’s unique synergy.
Our single atom alloy approach may in fact prove to be a general strategy for designing novel bi-functional heterogeneous catalysts in which a catalytically active element is atomically dispersed in a more inert matrix. Very recently we demonstrated that this strategy works in the design of real catalysts. Palladium/copper nanoparticles containing <2% palladium exhibited highly selective hydrogenation of phenylacetylene under realistic reaction conditions and platinum/copper nanoparticles perform the industrially important butadiene hydrogenation at lower temperature using just 1% platinum. Moreover, some of the best industrial alloy catalysts to date may already be operating via this mechanism, but there is currently no method to directly probe the atomic geometry of a working catalyst. Our scientific approach allows one to parse out the minimal reactive ensembles in an alloy catalyst and provide design rules for selective catalytic nanoparticle. From another practical application standpoint, the small amounts of precious metal required to produce single atom alloys generates a very attractive alternative to traditional bimetallic catalysts.