Manipulating the Geometric and Electronic Structures of Manganese Nitrides for Ammonia Synthesis

Shan, Nannan; Huang, Chaoran; Lee, Robert T.; Manavi, Narges; Xu, Lianbin; Chikan, Viktor; Pfromm, Peter Heinz; Liu, Bin

doi:10.1002/cctc.201902383

Title: Manipulating the Geometric and Electronic Structures of Manganese Nitrides for Ammonia Synthesis

Journal Article · 10 March 2020 · ChemCatChem

DOI: https://doi.org/10.1002/cctc.201902383 · OSTI ID:1615971

Shan, Nannan ^[1]; Huang, Chaoran ^[1]; Lee, Robert T. ^[1]; Manavi, Narges ^[1]; Xu, Lianbin ^[2]; Chikan, Viktor ^[3]; Pfromm, Peter Heinz ^[4];

^[1]

Tim Taylor Department of Chemical Engineering Kansas State University Manhattan KS 66506 USA
State Key Laboratory of Organic-Inorganic Composites Beijing University of Chemical Technology Beijing 100029 P.R. China
Department of Chemistry Kansas State University Manhattan KS 66506 USA
Tim Taylor Department of Chemical Engineering Kansas State University Manhattan KS 66506 USA, Voiland School of Chemical Engineering and Bioengineering Washington State University Pullman WA 99164 USA

Abstract Manganese (Mn) nitrides are important nitrogen (N) carriers for small‐scale intermittent ammonia (NH ₃ ) synthesis. However, only 3∼8 % of lattice N are converted into NH ₃ . In this study, the geometric and electronic structures of well‐defined Mn ₄ N and Mn ₂ N lattices were altered using transition metal heteroatoms (Cr, Fe, Co, Ni, Mo) to understand the driving force behind lattice N diffusion and extraction. Density Functional Theory (DFT) revealed that the binding of early hydrogenation product (NH) follows a linear relationship with lattice N over a wide range of close‐packed surfaces. But, the binding of NH ₂ and NH ₃ are more sensitive to the geometric and electronic structures. Further, the chemical bonding can be quantitatively characterized with the covalency derived from Crystal Orbital Hamiltonian Population (COHP). In the Eley Rideal‐Mars van Krevelan pathway, the overall NH ₃ formation free energy ( ) and lattice N diffusion barrier ( ) are the respective thermodynamic and kinetic determining factors. Aided by a rate‐determining step (RDS) model, Mn ₄ N modified with Fe, Co, Ni single‐atom dopants all show enhanced rates for NH ₃ formation.

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Sponsoring Organization:: USDOE

OSTI ID:: 1615971

Journal Information:: ChemCatChem, Journal Name: ChemCatChem Journal Issue: 8 Vol. 12; ISSN 1867-3880

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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