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

An, Qi and Mcdonald, Molly and Fortunelli, Alessandro and Goddard, William A., III (2021) Controlling the Shapes of Nanoparticles by Dopant-Induced Enhancement of Chemisorption and Catalytic Activity: Application to Fe-Based Ammonia Synthesis. ACS Nano, 15 (1). pp. 1675-1684. ISSN 1936-0851. doi:10.1021/acsnano.0c09346.

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We showed recently that the catalytic efficiency of ammonia synthesis on Fe-based nanoparticles (NP) for Haber–Bosch (HB) reduction of N₂ 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) vs 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.

Item Type:Article
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URLURL TypeDescription
An, Qi0000-0003-4838-6232
Fortunelli, Alessandro0000-0001-5337-4450
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2020 American Chemical Society. Received: November 8, 2020; Accepted: December 14, 2020; Published: December 23, 2020. M.M. was supported by NSF (Grant CMMI-1727428). A.F. gratefully acknowledges the contribution of the International Research Network IRN on Nanoalloys (CNRS). W.A.G. III thanks ONR (Grant N00014-18-1-2155) for support. The authors would like to acknowledge the support of Research & Innovation and the Cyberinfrastructure Team in the Office of Information Technology at the University of Nevada, Reno for facilitation and access to the Pronghorn High-Performance Computing Cluster. The authors declare no competing financial interest.
Funding AgencyGrant Number
Centre National de la Recherche Scientifique (CNRS)UNSPECIFIED
Office of Naval Research (ONR)N00014-18-1-2155
Subject Keywords:nanoparticle; catalyst; wulff construction; dft; high-throughput screening
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Record Number:CaltechAUTHORS:20201224-085806667
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Official Citation:Controlling the Shapes of Nanoparticles by Dopant-Induced Enhancement of Chemisorption and Catalytic Activity: Application to Fe-Based Ammonia Synthesis. Qi An, Molly McDonald, Alessandro Fortunelli, and William A. Goddard. ACS Nano 2021 15 (1), 1675-1684; DOI: 10.1021/acsnano.0c09346
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:107272
Deposited By: George Porter
Deposited On:04 Jan 2021 16:32
Last Modified:16 Nov 2021 19:01

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