Tuning crystal-phase of bimetallic single-nanoparticle for catalytic hydrogenation

Bimetallic nanoparticles afford geometric variation and electron redistribution via strong metal-metal interactions that substantially promote the activity and selectivity in catalysis. Quantitatively describing the atomic configuration of the catalytically active sites, however, is experimentally challenged by the averaging ensemble effect that is caused by the interplay between particle size and crystal-phase at elevated temperatures and under reactive gases. Here, we report that the intrinsic activity of the body-centered cubic PdCu nanoparticle, for acetylene hydrogenation, is one order of magnitude greater than that of the face-centered cubic one. This finding is based on precisely identifying the atomic structures of the active sites over the same-sized but crystal-phase-varied single-particles. The densely-populated Pd-Cu bond on the chemically ordered nanoparticle possesses isolated Pd site with a lower coordination number and a high-lying valence d-band center, and thus greatly expedites the dissociation of H-2 over Pd atom and efficiently accommodates the activated H atoms on the particle top/subsurfaces. Quantitatively describing the atomic configuration of the catalytically active sites is challenging. Here the authors demonstrate that tuning crystal-phase of metal single-particle enables to precisely describe the atomic structure of the active sites and accurately identify the activation routes of the reacting molecules.

Automated summary

Bimetallic nanoparticles with geometric variation and electron redistribution can greatly enhance catalytic activity and selectivity. However, quantitatively describing the atomic configuration of catalytically active sites is challenging due to the interplay between particle size and crystal phase. In this study, the authors demonstrate that tuning the crystal phase of metal single-particles allows for accurate description of the atomic structure of active sites.