Phosphorene‐Supported Transition‐Metal Dimer for Effective N 2 Electroreduction

Tang, Qing; Jiang, De‐en

doi:10.1002/cphc.201900279

Title: Phosphorene‐Supported Transition‐Metal Dimer for Effective N ₂ Electroreduction

Journal Article · 21 May 2019 · ChemPhysChem

DOI: https://doi.org/10.1002/cphc.201900279 · OSTI ID:1515115

^[1]; Jiang, De‐en ^[2]

School of Chemistry and Chemical Engineering Chongqing University Chongqing 401331 China
Department of Chemistry University of California Riverside, CA 92521 USA

Abstract The electrochemical reduction of N ₂ to NH ₃ at ambient conditions is a promising alternative to the energy‐intensive, high‐temperature, high‐pressure Haber‐Bosch process. But it is extremely challenging to find an electrocatalyst that can effectively activate N ₂ and reduce it to NH ₃ . From first principles density functional theory, we found that the Ti dimer supported on single‐layer phosphorene can be used as a promising electrocatalyst for N ₂ capture and conversion to NH ₃ . The overpotential (relative to the standard hydrogen electrode) was found to be as low as 0.20, much lower than those predicted on the Ti surface (1 to 1.5 V) or their nitrides (0.5 to 1 V). In addition, we found that hydride is involved in the N ₂ reduction on the Ti dimer catalyst via formation of Ti ₂ ‐H species, and the hydride would favorably transfer onto the adsorbed N ₂ * to form *NNH intermediate and further reduced to NH ₃ . Moreover, we also examined other first‐row transition metal dimers, and found that Sc and Fe dimer to be potential catalysts which could catalyze N ₂ reduction at a low overpotential of about 0.21 and 0.45 V, respectively. Our predictions hence suggest Ti, Sc and Fe dimer clusters supported on phosphorene as promising electrocatalysts for N ₂ reduction to NH ₃ .

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Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1515115

Journal Information:: ChemPhysChem, Journal Name: ChemPhysChem Journal Issue: 22 Vol. 20; ISSN 1439-4235

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

Country of Publication:: Germany

Language:: English

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Title: Phosphorene‐Supported Transition‐Metal Dimer for Effective N ₂ Electroreduction