Controlling the Shapes of Nanoparticles by Dopant-Induced Enhancement of Chemisorption and Catalytic Activity: Application to Fe-Based Ammonia Synthesis.

We showed recently that the catalytic efficiency of ammonia synthesis on Fe-based nanoparticles (NP) for Haber-Bosch (HB) reduction of N to ammonia depends very dramatically on the crystal surface exposed and on the doping. In turn, the stability of each surface depends on the stable intermediates present during the catalysis. Thus, under reaction conditions, the shape of the NP is expected to evolve to optimize surface energies. In this paper, we propose to manipulate the shape of the nanoparticles through doping combined with chemisorption and catalysis. To do this, we consider the relationships between the catalyst composition (adding dopant elements) and on how the distribution of the dopant atoms on the bulk and facet sites affects the shape of the particles and therefore the number of active sites on the catalyst surfaces. We use our hierarchical, high-throughput catalyst screening (HHTCS) approach but extend the scope of HHTCS to select dopants that can increase the catalytically active surface orientations, such as Fe-bcc(111), at the expense of catalytically inactive facets, such as Fe-bcc(100). Then, for the most promising dopants, we predict the resulting shape and activity of doped Fe-based nanoparticles under reaction conditions. We examined 34 possible dopants across the periodic table and found 16 dopants that can potentially increase the fraction of active Fe-bcc(111) inactive Fe-bcc(100) facets. Combining this reshaping criterion with our HHTCS estimate of the resulting catalytic performance, we show that Si and Ni are the most promising elements for improving the rates of catalysis by optimizing the shape to decrease reaction barriers. Then, using Si dopant as a working example, we build a steady-state dynamical Wulff construction of Si-doped Fe bcc nanoparticles. We use nanoparticles with a diameter of ∼10 nm, typical of industrial catalysts. We predict that doping Si into such Fe nanoparticles at the optimal atomic content of ∼0.3% leads to rate enhancements by a factor of 56 per nanoparticle under target HB conditions.