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Title: Computational Design of Active Site Structures with Improved Transition-State Scaling for Ammonia Synthesis

Journal Article · · ACS Catalysis
ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [2];  [3]
  1. Stanford Univ., Stanford, CA (United States)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States); Univ. of Pennsylvania, Philadelphia, PA (United States)
  3. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
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Here, the Haber–Bosch process for the reduction of atmospheric nitrogen to ammonia is one of the most optimized heterogeneous catalytic reactions, but there are aspects of the industrial process that remain less than ideal. It has been shown that the activity of metal catalysts is limited by a Brønsted–Evans–Polanyi (BEP) scaling relationship between the reaction and transition-state energies for N2 dissociation, leading to a negligible production rate at ambient conditions and a modest rate under harsh conditions. In this study, we use density functional theory (DFT) calculations in conjunction with mean-field microkinetic modeling to study the rate of NH3 synthesis on model active sites that require the singly coordinated dissociative adsorption of N atoms onto transition metal atoms. Our results demonstrate that this ”on-top” binding of nitrogen exhibits significantly improved scaling behavior, which can be rationalized in terms of transition-state geometries and leads to considerably higher predicted activity. While synthesis of these model systems is likely challenging, the stabilization of such an active site could enable thermochemical ammonia synthesis under more benign conditions.

Research Organization:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
DGE-1656518; 9455; AC02-76SF00515
OSTI ID:
1459599
Journal Information:
ACS Catalysis, Vol. 8, Issue 5; ISSN 2155-5435
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 55 works
Citation information provided by
Web of Science

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Cited By (4)

Recent advances in metal sulfides: from controlled fabrication to electrocatalytic, photocatalytic and photoelectrochemical water splitting and beyond journal January 2019
Catalytic resonance theory: superVolcanoes, catalytic molecular pumps, and oscillatory steady state journal January 2019
Atomically Dispersed Single Ni Site Catalysts for Nitrogen Reduction toward Electrochemical Ammonia Synthesis Using N 2 and H 2 O journal February 2020
Theoretical design of a technetium-like alloy and its catalytic properties journal January 2019

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ammonia synthesis
density functional theory
microkinetic modeling
scaling relations
transition states