Ammonia Synthesis via an Associative Mechanism on Alkaline Earth Metal Sites of Ca3CrN3H

Yu Cao; Ekaterina Toshcheva; Walid Almaksoud; Rafia Ahmad; Tatsuya Tsumori; Rohit Rai; Ya Tang; Luigi Cavallo; Hiroshi Kageyama; Yoji Kobayashi

doi:10.1002/cssc.202300234

Ammonia Synthesis via an Associative Mechanism on Alkaline Earth Metal Sites of Ca₃CrN₃H

Yu Cao, Ekaterina Toshcheva, Walid Almaksoud, Rafia Ahmad, Tatsuya Tsumori, Rohit Rai, Ya Tang, Luigi Cavallo, Hiroshi Kageyama^*, Yoji Kobayashi^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

7 Scopus citations

Abstract

Typically, transition metals are considered as the centers for the activation of dinitrogen. Here we demonstrate that the nitride hydride compound Ca₃CrN₃H, with robust ammonia synthesis activity, can activate dinitrogen through active sites where calcium provides the primary coordination environment. DFT calculations also reveal that an associative mechanism is favorable, distinct from the dissociative mechanism found in traditional Ru or Fe catalysts. This work shows the potential of alkaline earth metal hydride catalysts and other related 1 D hydride/electrides for ammonia synthesis.

Original language	English (US)
Article number	e202300234
Journal	CHEMSUSCHEM
Volume	16
Issue number	22
DOIs	https://doi.org/10.1002/cssc.202300234
State	Accepted/In press - 2023

Keywords

density functional calculations
heterogeneous catalysis
hydrides
mixed anions
nitrogen reduction reaction

ASJC Scopus subject areas

Environmental Chemistry
General Chemical Engineering
General Materials Science
General Energy

Access to Document

10.1002/cssc.202300234

Cite this

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title = "Ammonia Synthesis via an Associative Mechanism on Alkaline Earth Metal Sites of Ca3CrN3H",

abstract = "Typically, transition metals are considered as the centers for the activation of dinitrogen. Here we demonstrate that the nitride hydride compound Ca3CrN3H, with robust ammonia synthesis activity, can activate dinitrogen through active sites where calcium provides the primary coordination environment. DFT calculations also reveal that an associative mechanism is favorable, distinct from the dissociative mechanism found in traditional Ru or Fe catalysts. This work shows the potential of alkaline earth metal hydride catalysts and other related 1 D hydride/electrides for ammonia synthesis.",

keywords = "density functional calculations, heterogeneous catalysis, hydrides, mixed anions, nitrogen reduction reaction",

author = "Yu Cao and Ekaterina Toshcheva and Walid Almaksoud and Rafia Ahmad and Tatsuya Tsumori and Rohit Rai and Ya Tang and Luigi Cavallo and Hiroshi Kageyama and Yoji Kobayashi",

note = "Funding Information: This work was supported by the Japan Society for Promotion of Science (JSPS) the Grant‐in‐Aid for Specially Promoted Research (22H04914), JSPS Core‐to‐Core Program (Grant JPJSCCA20200004), CREST (JPMJCR20R2) and JSPS KAKENHI (21J15834). Financial support for this work was also provided by the King Abdullah University of Science and Technology (KAUST). The synchrotron X‐ray diffraction measurements were carried out by the project approval (nos. 2021 A1595 and 2021B1815). Publisher Copyright: {\textcopyright} 2023 Wiley-VCH GmbH.",

year = "2023",

doi = "10.1002/cssc.202300234",

language = "English (US)",

volume = "16",

journal = "CHEMSUSCHEM",

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T1 - Ammonia Synthesis via an Associative Mechanism on Alkaline Earth Metal Sites of Ca3CrN3H

AU - Cao, Yu

AU - Toshcheva, Ekaterina

AU - Almaksoud, Walid

AU - Ahmad, Rafia

AU - Tsumori, Tatsuya

AU - Rai, Rohit

AU - Tang, Ya

AU - Cavallo, Luigi

AU - Kageyama, Hiroshi

AU - Kobayashi, Yoji

N1 - Funding Information: This work was supported by the Japan Society for Promotion of Science (JSPS) the Grant‐in‐Aid for Specially Promoted Research (22H04914), JSPS Core‐to‐Core Program (Grant JPJSCCA20200004), CREST (JPMJCR20R2) and JSPS KAKENHI (21J15834). Financial support for this work was also provided by the King Abdullah University of Science and Technology (KAUST). The synchrotron X‐ray diffraction measurements were carried out by the project approval (nos. 2021 A1595 and 2021B1815). Publisher Copyright: © 2023 Wiley-VCH GmbH.

PY - 2023

Y1 - 2023

N2 - Typically, transition metals are considered as the centers for the activation of dinitrogen. Here we demonstrate that the nitride hydride compound Ca3CrN3H, with robust ammonia synthesis activity, can activate dinitrogen through active sites where calcium provides the primary coordination environment. DFT calculations also reveal that an associative mechanism is favorable, distinct from the dissociative mechanism found in traditional Ru or Fe catalysts. This work shows the potential of alkaline earth metal hydride catalysts and other related 1 D hydride/electrides for ammonia synthesis.

AB - Typically, transition metals are considered as the centers for the activation of dinitrogen. Here we demonstrate that the nitride hydride compound Ca3CrN3H, with robust ammonia synthesis activity, can activate dinitrogen through active sites where calcium provides the primary coordination environment. DFT calculations also reveal that an associative mechanism is favorable, distinct from the dissociative mechanism found in traditional Ru or Fe catalysts. This work shows the potential of alkaline earth metal hydride catalysts and other related 1 D hydride/electrides for ammonia synthesis.

KW - density functional calculations

KW - heterogeneous catalysis

KW - hydrides

KW - mixed anions

KW - nitrogen reduction reaction

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