Descriptors and graphical construction for in silico design of efficient and selective single atom catalysts for eNRR

Abstract

The electrochemical nitrogen reduction reaction (eNRR) offers the possibility of ammonia synthesis under mild conditions; however, it suffers from low yields, a competing hydrogen evolution reaction pathway, and hydrogen poisoning. We present a systematic approach toward screening single atom catalysts (SACs) for eNRR, by focusing on key parameters computed from density functional theory, and relationships between them. We illustrate this by application to 66 model catalysts of the types, TM-Pc, TM-NXCY, and TM-N3, where TM is a 3d transition metal or molybdenum. We identified the best SACs as Sc-Pc, Cr-N4, Mn-Pc, and Fe-N2C2; these show eNRR selectivity over HER and no hydrogen poisoning. The catalysts are identified through multi-parameter optimization which includes the condition of hydrogen poisoning. We propose a new electronic descriptor Oval, the valence electron occupancy of the metal center, that exhibits a volcano-type relationship with eNRR overpotential. Our multi-parameter optimization approach can be mapped onto a simple graphical construction to find the best catalyst for eNRR over HER and hydrogen poisoning.

Supplementary files

Article information

Article type
Edge Article
Submitted
11 May 2022
Accepted
05 Aug 2022
First published
05 Aug 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2022, Accepted Manuscript

Descriptors and graphical construction for in silico design of efficient and selective single atom catalysts for eNRR

S. Kapse, S. Narasimhan and R. Thapa, Chem. Sci., 2022, Accepted Manuscript , DOI: 10.1039/D2SC02625B

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