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

Singh, Aayush R.; Montoya, Joseph H.; Rohr, Brian A.; Tsai, Charlie; Vojvodic, Aleksandra; Norskov, Jens K.

doi:10.1021/acscatal.8b00106

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

Journal Article · Fri Mar 30 00:00:00 EDT 2018 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.8b00106· OSTI ID:1459599

^[1]; Montoya, Joseph H. ^[1]; Rohr, Brian A. ^[1]; Tsai, Charlie ^[1]; ^[2]; Norskov, Jens K. ^[3]

Stanford Univ., Stanford, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States); Univ. of Pennsylvania, Philadelphia, PA (United States)
Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1459599

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 5 Vol. 8; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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