Low-Temperature Synthesis of Perovskite Oxynitride-Hydrides as Ammonia Synthesis Catalysts

Masaaki Kitano, Jun Kujirai, Kiya Ogasawara, Satoru Matsuishi, Tomofumi Tada, Hitoshi Abe, Yasuhiro Niwa, Hideo Hosono

Research output: Contribution to journalArticle

Abstract

Mixed anionic materials such as oxyhydrides and oxynitrides have recently attracted significant attention due to their unique properties, such as fast hydride ion conduction, enhanced ferroelectrics, and catalytic activity. However, high temperature (≥800 °C) and/or complicated processes are required for the synthesis of these compounds. Here we report that a novel perovskite oxynitride-hydride, BaCeO3-xNyHz, can be directly synthesized by the reaction of CeO2 with Ba(NH2)2 at low temperatures (300-600 °C). BaCeO3-xNyHz, with and without transition metal nanoparticles, functions as an efficient catalyst for ammonia synthesis through the lattice N3- and H- ion-mediated Mars-van Krevelen mechanism, while ammonia synthesis occurs over conventional catalysts through a Langmuir-Hinshelwood mechanism with high energy barriers (85-121 kJ mol-1). As a consequence, the unique reaction mechanism leads to enhancement of the activity of BaCeO3-based catalysts by a factor of 8-218 and lowers the activation energy (46-62 kJ mol-1) for ammonia synthesis. Furthermore, isotopic experiments reveal that this catalyst shifts the rate-determining step for ammonia synthesis from N2 dissociation to N-H bond formation.

Original languageEnglish
Pages (from-to)20344-20353
Number of pages10
JournalJournal of the American Chemical Society
Volume141
Issue number51
DOIs
Publication statusPublished - Dec 26 2019

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Ammonia
Hydrides
Perovskite
Catalysts
Temperature
Metal Nanoparticles
Ions
Mars
Metal nanoparticles
Energy barriers
Ferroelectric materials
Transition metals
Catalyst activity
Activation energy
perovskite
Experiments

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Low-Temperature Synthesis of Perovskite Oxynitride-Hydrides as Ammonia Synthesis Catalysts. / Kitano, Masaaki; Kujirai, Jun; Ogasawara, Kiya; Matsuishi, Satoru; Tada, Tomofumi; Abe, Hitoshi; Niwa, Yasuhiro; Hosono, Hideo.

In: Journal of the American Chemical Society, Vol. 141, No. 51, 26.12.2019, p. 20344-20353.

Research output: Contribution to journalArticle

Kitano, M, Kujirai, J, Ogasawara, K, Matsuishi, S, Tada, T, Abe, H, Niwa, Y & Hosono, H 2019, 'Low-Temperature Synthesis of Perovskite Oxynitride-Hydrides as Ammonia Synthesis Catalysts', Journal of the American Chemical Society, vol. 141, no. 51, pp. 20344-20353. https://doi.org/10.1021/jacs.9b10726
Kitano, Masaaki ; Kujirai, Jun ; Ogasawara, Kiya ; Matsuishi, Satoru ; Tada, Tomofumi ; Abe, Hitoshi ; Niwa, Yasuhiro ; Hosono, Hideo. / Low-Temperature Synthesis of Perovskite Oxynitride-Hydrides as Ammonia Synthesis Catalysts. In: Journal of the American Chemical Society. 2019 ; Vol. 141, No. 51. pp. 20344-20353.
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