Photochemical Acceleration of Ammonia Production by Pt1-Ptn-TiN Reduction and N2 Activation

Chengliang Mao; Jiaxian Wang; Yunjie Zou; Yanbiao Shi; Camilo J. Viasus; Joel Y.Y. Loh; Meikun Xia; Shufang Ji; Meiqi Li; Huan Shang; Mireille Ghoussoub; Yang Fan Xu; Jessica Ye; Zhilin Li; Nazir P. Kherani; Lirong Zheng; Yanjiang Liu; Lizhi Zhang; Geoffrey A. Ozin

doi:10.1021/jacs.3c01947

Photochemical Acceleration of Ammonia Production by Pt₁-Pt_n-TiN Reduction and N₂ Activation

Chengliang Mao, Jiaxian Wang, Yunjie Zou, Yanbiao Shi, Camilo J. Viasus, Joel Y.Y. Loh, Meikun Xia, Shufang Ji, Meiqi Li, Huan Shang, Mireille Ghoussoub, Yang Fan Xu, Jessica Ye, Zhilin Li, Nazir P. Kherani, Lirong Zheng^*, Yanjiang Liu, Lizhi Zhang^*, Geoffrey A. Ozin^*

^*Corresponding author for this work

EEE - Academic & Research

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

Abstract

Stable metal nitrides (MN) are promising materials to fit the future “green” ammonia-hydrogen nexus. Either through catalysis or chemical looping, the reductive hydrogenation of MN to MN_1-x is a necessary step to generate ammonia. However, encumbered by the formation of kinetically stable M-NH_1─3 surface species, this reduction step remains challenging under mild conditions. Herein, we discovered that deleterious Ti-NH_1─3 accumulation on TiN can be circumvented photochemically with supported single atoms and clusters of platinum (Pt₁-Pt_n) under N₂-H₂ conditions. The photochemistry of TiN selectively promoted Ti-NH formation, while Pt₁-Pt_n effectively transformed any formed Ti-NH into free ammonia. The generated ammonia was found to originate mainly from TiN reduction with a minor contribution from N₂ activation. The knowledge accrued from this fundamental study could serve as a springboard for the development of MN materials for more efficient ammonia production to potentially disrupt the century-old fossil-powered Haber-Bosch process.

Original language	English
Pages (from-to)	13134-13146
Number of pages	13
Journal	Journal of the American Chemical Society
Volume	145
Issue number	24
DOIs	https://doi.org/10.1021/jacs.3c01947
Publication status	Published - 21 Jun 2023

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Mao, C., Wang, J., Zou, Y., Shi, Y., Viasus, C. J., Loh, J. Y. Y., Xia, M., Ji, S., Li, M., Shang, H., Ghoussoub, M., Xu, Y. F., Ye, J., Li, Z., Kherani, N. P., Zheng, L., Liu, Y., Zhang, L., & Ozin, G. A. (2023). Photochemical Acceleration of Ammonia Production by Pt₁-Pt_n-TiN Reduction and N₂ Activation. Journal of the American Chemical Society, 145(24), 13134-13146. https://doi.org/10.1021/jacs.3c01947

@article{619f6eb44c13423a966b24a5303019f2,

title = "Photochemical Acceleration of Ammonia Production by Pt1-Ptn-TiN Reduction and N2 Activation",

abstract = "Stable metal nitrides (MN) are promising materials to fit the future “green” ammonia-hydrogen nexus. Either through catalysis or chemical looping, the reductive hydrogenation of MN to MN1-x is a necessary step to generate ammonia. However, encumbered by the formation of kinetically stable M-NH1─3 surface species, this reduction step remains challenging under mild conditions. Herein, we discovered that deleterious Ti-NH1─3 accumulation on TiN can be circumvented photochemically with supported single atoms and clusters of platinum (Pt1-Ptn) under N2-H2 conditions. The photochemistry of TiN selectively promoted Ti-NH formation, while Pt1-Ptn effectively transformed any formed Ti-NH into free ammonia. The generated ammonia was found to originate mainly from TiN reduction with a minor contribution from N2 activation. The knowledge accrued from this fundamental study could serve as a springboard for the development of MN materials for more efficient ammonia production to potentially disrupt the century-old fossil-powered Haber-Bosch process.",

author = "Chengliang Mao and Jiaxian Wang and Yunjie Zou and Yanbiao Shi and Viasus, {Camilo J.} and Loh, {Joel Y.Y.} and Meikun Xia and Shufang Ji and Meiqi Li and Huan Shang and Mireille Ghoussoub and Xu, {Yang Fan} and Jessica Ye and Zhilin Li and Kherani, {Nazir P.} and Lirong Zheng and Yanjiang Liu and Lizhi Zhang and Ozin, {Geoffrey A.}",

note = "Publisher Copyright: {\textcopyright} 2023 American Chemical Society.",

year = "2023",

month = jun,

day = "21",

doi = "10.1021/jacs.3c01947",

language = "English",

volume = "145",

pages = "13134--13146",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "24",

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Mao, C, Wang, J, Zou, Y, Shi, Y, Viasus, CJ, Loh, JYY, Xia, M, Ji, S, Li, M, Shang, H, Ghoussoub, M, Xu, YF, Ye, J, Li, Z, Kherani, NP, Zheng, L, Liu, Y, Zhang, L & Ozin, GA 2023, 'Photochemical Acceleration of Ammonia Production by Pt₁-Pt_n-TiN Reduction and N₂ Activation', Journal of the American Chemical Society, vol. 145, no. 24, pp. 13134-13146. https://doi.org/10.1021/jacs.3c01947

TY - JOUR

T1 - Photochemical Acceleration of Ammonia Production by Pt1-Ptn-TiN Reduction and N2 Activation

AU - Mao, Chengliang

AU - Wang, Jiaxian

AU - Zou, Yunjie

AU - Shi, Yanbiao

AU - Viasus, Camilo J.

AU - Loh, Joel Y.Y.

AU - Xia, Meikun

AU - Ji, Shufang

AU - Li, Meiqi

AU - Shang, Huan

AU - Ghoussoub, Mireille

AU - Xu, Yang Fan

AU - Ye, Jessica

AU - Li, Zhilin

AU - Kherani, Nazir P.

AU - Zheng, Lirong

AU - Liu, Yanjiang

AU - Zhang, Lizhi

AU - Ozin, Geoffrey A.

PY - 2023/6/21

Y1 - 2023/6/21

N2 - Stable metal nitrides (MN) are promising materials to fit the future “green” ammonia-hydrogen nexus. Either through catalysis or chemical looping, the reductive hydrogenation of MN to MN1-x is a necessary step to generate ammonia. However, encumbered by the formation of kinetically stable M-NH1─3 surface species, this reduction step remains challenging under mild conditions. Herein, we discovered that deleterious Ti-NH1─3 accumulation on TiN can be circumvented photochemically with supported single atoms and clusters of platinum (Pt1-Ptn) under N2-H2 conditions. The photochemistry of TiN selectively promoted Ti-NH formation, while Pt1-Ptn effectively transformed any formed Ti-NH into free ammonia. The generated ammonia was found to originate mainly from TiN reduction with a minor contribution from N2 activation. The knowledge accrued from this fundamental study could serve as a springboard for the development of MN materials for more efficient ammonia production to potentially disrupt the century-old fossil-powered Haber-Bosch process.

AB - Stable metal nitrides (MN) are promising materials to fit the future “green” ammonia-hydrogen nexus. Either through catalysis or chemical looping, the reductive hydrogenation of MN to MN1-x is a necessary step to generate ammonia. However, encumbered by the formation of kinetically stable M-NH1─3 surface species, this reduction step remains challenging under mild conditions. Herein, we discovered that deleterious Ti-NH1─3 accumulation on TiN can be circumvented photochemically with supported single atoms and clusters of platinum (Pt1-Ptn) under N2-H2 conditions. The photochemistry of TiN selectively promoted Ti-NH formation, while Pt1-Ptn effectively transformed any formed Ti-NH into free ammonia. The generated ammonia was found to originate mainly from TiN reduction with a minor contribution from N2 activation. The knowledge accrued from this fundamental study could serve as a springboard for the development of MN materials for more efficient ammonia production to potentially disrupt the century-old fossil-powered Haber-Bosch process.

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U2 - 10.1021/jacs.3c01947

DO - 10.1021/jacs.3c01947

M3 - Article

C2 - 37278596

AN - SCOPUS:85162869422

SN - 0002-7863

VL - 145

SP - 13134

EP - 13146

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 24

ER -

Photochemical Acceleration of Ammonia Production by Pt₁-Pt_n-TiN Reduction and N₂ Activation

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