Ring-opening and hydrodenitrogenation of indole under hydrothermal conditions over Ni, Pt, Ru, and Ni-Ru bimetallic catalysts

Guo, Yang; He, Haoran; Liu, Xu; Chen, Zhifeng; Rioux, Robert M.; Janik, Michael J.; Savage, Phillip E.

doi:10.1016/j.cej.2020.126853

Ring-opening and hydrodenitrogenation of indole under hydrothermal conditions over Ni, Pt, Ru, and Ni-Ru bimetallic catalysts

Journal Article · Thu Sep 03 00:00:00 EDT 2020 · Chemical Engineering Journal

DOI:https://doi.org/10.1016/j.cej.2020.126853· OSTI ID:1852119

Guo, Yang ^[1]; He, Haoran ^[2]; Liu, Xu ^[3]; Chen, Zhifeng ^[2]; Rioux, Robert M. ^[2]; Janik, Michael J. ^[2]; Savage, Phillip E. ^[2]

Xi'an Jiaotong Univ., Shaanxi (China); Pennsylvania State Univ., University Park, PA (United States); Xi'an Jiaotong University Suzhou Academy (China); Pennsylvania State Univ., University Park, PA (United States)
Pennsylvania State Univ., University Park, PA (United States)
Xi'an Jiaotong Univ., Shaanxi (China)

Here, the activity and selectivity of activated-carbon-supported Ni, Pt, Ru, and Ni-Ru bimetallic catalysts was examined for hydrothermal denitrogenation of indole. The molar yield of pyrrole ring-opening compounds, without an added hydrogen source, are in the order: Ni < Pt < Ni₉₀Ru₁₀ < Ni₇₅Ru₂₅ < Ni₅₀Ru₅₀ ~ Ni₂₅Ru₇₅ ~ Ru. Ru-containing catalysts facilitated production of hydrocarbons (hydrodenitrogenation (HDN) products) when used with added formic acid (hydrogen source). We elucidated catalytic hydrothermal HDN pathways for indole based on the product distributions and the variation of their yields with time. Hydrogenation of indole to indoline is the primary pathway and ring-opening of indoline to form alkyl anilines is faster than forming HDN products (alkyl benzenes). DFT calculations confirmed experimental activity trends, showing Ru is more active than Ni for indole ring opening and for o-toluidine deamination. If no hydrogen source is present, directly breaking the N-C bond in the pyrrole ring is more favorable than breaking the C-N bond with an aromatic carbon. If a H source is provided, the pyrrole ring hydrogenates first, forming indoline, followed by cleavage of the C-N bond.

View Accepted Manuscript (DOE)

Research Organization:: Pennsylvania State Univ., University Park, PA (United States)

Sponsoring Organization:: Jiangsu Province Natural Science Foundation of China; National Natural Science Foundation of China; Shaanxi Province Natural Science Foundation of China; USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0016192

OSTI ID:: 1852119

Alternate ID(s):: OSTI ID: 1780312

Journal Information:: Chemical Engineering Journal, Journal Name: Chemical Engineering Journal Journal Issue: C Vol. 406; ISSN 1385-8947

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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bimetallic
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Ring-opening and hydrodenitrogenation of indole under hydrothermal conditions over Ni, Pt, Ru, and Ni-Ru bimetallic catalysts

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