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Highly Efficient Ni-Doped Iron Catalyst for Ammonia Synthesis from QM-Based Hierarchical High Throughput Catalyst Screening

Mcdonald, Molly and Fuller, Jon and Fortunelli, Alessandro and Goddard, William A. and An, Qi (2019) Highly Efficient Ni-Doped Iron Catalyst for Ammonia Synthesis from QM-Based Hierarchical High Throughput Catalyst Screening. Journal of Physical Chemistry C, 123 (28). pp. 17375-17383. ISSN 1932-7447. doi:10.1021/acs.jpcc.9b04386.

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To discover more efficient industrial catalysts for ammonia synthesis via the Haber–Bosch (HB) process, we employed quantum mechanics (QM)-based hierarchical high-throughput catalyst screening (HHTCS) to test a wide group of elements (34) as candidates to dope the Fe(111) catalyst subsurface. The QM free-energy reaction network of HB over Fe(111) yields ten barriers as potentially rate-determining, of which we select four as prototypical, arrange them hierarchically, and define a corresponding set of screening criteria, which we then use to screen candidate catalysts. This leads to two promising candidates (Co and Ni), from which we selected the most promising (Ni) for a complete QM and kinetic study. The kinetic Monte Carlo (kMC) simulations predict a 16-fold increase in HB turn-over frequency (TOF) for the Ni-doped catalyst compared to the pure Fe(111) surface under realistic conditions. The 16-fold increase in HB TOF is a significant improvement and may trigger future experimental studies to validate our prediction. This TOF improvement could lead to similar reaction rates as with pure Fe but at a reaction temperature decreased by 100° from 773 to 673 K and a total reactant pressure decreased by 6 times from 201 to 34 atm. We interpret the reasons underlying this improvement using valence bond and kinetic analyses. We suggest this Ni-doped Fe(111) catalyst as a candidate to reduce the world energy consumption for the HB process while satisfying future needs for energy and environment.

Item Type:Article
Related URLs:
URLURL TypeDescription
Fuller, Jon0000-0003-1233-7842
Fortunelli, Alessandro0000-0001-5337-4450
Goddard, William A.0000-0003-0097-5716
An, Qi0000-0003-4838-6232
Additional Information:© 2019 American Chemical Society. Received: May 8, 2019; Revised: June 15, 2019; Published: June 20, 2019. This work was initiated by the U.S. Department of Energy (USDOE), Office of Energy Efficiency and Renewable Energy (EERE), Advanced Manufacturing Office Next Generation R&D Projects under contract no. DE-AC07-05ID14517 (program manager Dickson Ozokwelu, in collaboration with Idaho National Laboratories, Rebecca Fushimi). We would like to thank the Information Technology department at the University of Nevada, Reno for computing time on the High Performance Computing Cluster (Pronghorn). Some calculations were also carried out on the GPU-cluster at Caltech provided by DURIP (Cliff Bedford, program manager). Some simulations were also performed on National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy Office of Science User Facility operated under Contract No. DE-AC02-05CH11231. The authors declare no competing financial interest.
Group:Astronomy Department
Funding AgencyGrant Number
Department of Energy (DOE)DE-AC07-05ID14517
Department of Energy (DOE)DE-AC02-05CH11231
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Issue or Number:28
Record Number:CaltechAUTHORS:20190620-151929496
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Official Citation:Highly Efficient Ni-Doped Iron Catalyst for Ammonia Synthesis from Quantum-Mechanics-Based Hierarchical High-Throughput Catalyst Screening. Molly Mcdonald, Jon Fuller, Alessandro Fortunelli, William A. Goddard III, and Qi An. The Journal of Physical Chemistry C 2019 123 (28), 17375-17383. DOI: 10.1021/acs.jpcc.9b04386
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:96606
Deposited By: Tony Diaz
Deposited On:20 Jun 2019 22:24
Last Modified:16 Nov 2021 17:22

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