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

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

References (40)

Effect of the damping function in dispersion corrected density functional theory Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars Journal of Computational Chemistry, Vol. 32, Issue 7 https://doi.org/10.1002/jcc.21759	journal	March 2011
A study of ruthenium in zeolite-Y by X-ray photoelectron spectroscopy Pedersen, L. Journal of Catalysis, Vol. 61, Issue 1 https://doi.org/10.1016/0021-9517(80)90337-1	journal	January 1980
Photoelectron-spectroscopic study of nickel, manganese and cobalt selenides Mandale, A. B.; Badrinarayanan, S.; Date, S. K. Journal of Electron Spectroscopy and Related Phenomena, Vol. 33, Issue 1 https://doi.org/10.1016/0368-2048(84)80006-7	journal	January 1984
Characterization of alumina supported nickel-ruthenium systems Rynkowski, J.; Paryjczak, T.; Lenik, M. Applied Catalysis A: General, Vol. 126, Issue 2 https://doi.org/10.1016/0926-860X(95)00035-6	journal	June 1995
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Ruthenium promoted hydrodenitrogenation catalysts Hirschon, A. S.; Wilson, R. B.; Laine, R. M. Applied Catalysis, Vol. 34 https://doi.org/10.1016/S0166-9834(00)82464-1	journal	January 1987
Spectroscopic characterization of Al2O3-Ni selective absorbers for solar collectors Süzer, S. Solar Energy Materials and Solar Cells, Vol. 52, Issue 1-2 https://doi.org/10.1016/S0927-0248(97)00270-5	journal	March 1998
Effect of low temperature hydrothermal liquefaction on catalytic hydrodenitrogenation of algae biocrude and model macromolecules Costanzo, William; Hilten, Roger; Jena, Umakanta Algal Research, Vol. 13 https://doi.org/10.1016/j.algal.2015.11.009	journal	January 2016
Silica deposition as an approach for improving the hydrothermal stability of an alumina support during glycerol aqueous phase reforming Liu, Fang; Okolie, Chukwuemeka; Ravenelle, Ryan M. Applied Catalysis A: General, Vol. 551 https://doi.org/10.1016/j.apcata.2017.11.025	journal	February 2018
Catalytic hydrothermal hydrodenitrogenation of pyridine Duan, Peigao; Savage, Phillip E. Applied Catalysis B: Environmental, Vol. 108-109 https://doi.org/10.1016/j.apcatb.2011.08.007	journal	October 2011
Structure-reactivity relationship in catalytic hydrogenation of heterocyclic compounds over ruthenium black-Part A: Effect of substitution of pyrrole ring and side chain in N-heterocycles Eblagon, Katarzyna Morawa; Tsang, S. C. Edman Applied Catalysis B: Environmental, Vol. 160-161 https://doi.org/10.1016/j.apcatb.2014.04.044	journal	November 2014
Catalytic gasification of indole in supercritical water Guo, Yang; Wang, Shuzhong; Yeh, Thomas Applied Catalysis B: Environmental, Vol. 166-167 https://doi.org/10.1016/j.apcatb.2014.11.033	journal	May 2015
Potential yields and properties of oil from the hydrothermal liquefaction of microalgae with different biochemical content Biller, P.; Ross, A. B. Bioresource Technology, Vol. 102, Issue 1 https://doi.org/10.1016/j.biortech.2010.06.028	journal	January 2011
Supercritical water gasification of an aqueous by-product from biomass hydrothermal liquefaction with novel Ru modified Ni catalysts Zhang, Linghong; Champagne, Pascale; (Charles) Xu, Chunbao Bioresource Technology, Vol. 102, Issue 17, p. 8279-8287 https://doi.org/10.1016/j.biortech.2011.06.051	journal	September 2011
Support effect and metals interactions for NiRu/Al 2 O 3 , TiO 2 and ZrO 2 catalysts in the hydrodeoxygenation of phenol Valdés-Martínez, O. U.; Suárez-Toriello, V. A.; Reyes, J. A. de los Catalysis Today, Vol. 296 https://doi.org/10.1016/j.cattod.2017.04.007	journal	November 2017
Study on deactivation of Ni/Al2O3 catalyst for liquid phase hydrogenation of crude 1,4-butanediol aqueous solution Li, Haitao; Zhao, Yongxiang; Gao, Chunguang Chemical Engineering Journal, Vol. 181-182 https://doi.org/10.1016/j.cej.2011.06.029	journal	February 2012
Catalytic denitrogenation of hydrocarbons through partial oxidation in supercritical water Yuan, Pei-Qing; Cheng, Zhen-Min; Zhang, Xiang-Yang Fuel, Vol. 85, Issue 3 https://doi.org/10.1016/j.fuel.2005.07.006	journal	February 2006
Screening of supported transition metal catalysts for hydrogen production from glucose via catalytic supercritical water gasification Zhang, Linghong; Champagne, Pascale; Xu, Chunbao (Charles) International Journal of Hydrogen Energy, Vol. 36, Issue 16 https://doi.org/10.1016/j.ijhydene.2011.05.077	journal	August 2011
Long-term durability of Ni/TiO2 and Ru–Ni/TiO2 catalysts for selective CO methanation Tada, Shohei; Kikuchi, Ryuji; Wada, Katsuya Journal of Power Sources, Vol. 264 https://doi.org/10.1016/j.jpowsour.2014.04.075	journal	October 2014
Ru nanoparticles stabilized by poly(N-vinyl-2-pyrrolidone) grafted onto silica: Very active and stable catalysts for hydrogenation of aromatics Zhou, Xiaosi; Wu, Tianbin; Hu, Baoji Journal of Molecular Catalysis A: Chemical, Vol. 306, Issue 1-2 https://doi.org/10.1016/j.molcata.2009.03.002	journal	July 2009
Hydrothermal reaction of tryptophan over Ni-based bimetallic catalysts Guo, Yang; Chen, Zhifeng; Rioux, Robert M. The Journal of Supercritical Fluids, Vol. 143 https://doi.org/10.1016/j.supflu.2018.09.006	journal	January 2019
Supercritical water gasification of phenol over Ni-Ru bimetallic catalysts Zhang, Jiandong; Dasgupta, Anish; Chen, Zhifeng Water Research, Vol. 152 https://doi.org/10.1016/j.watres.2018.12.030	journal	April 2019
High Yield of Hydrocarbons from Catalytic Hydrodenitrogenation of Indole under Hydrothermal Conditions Luo, Ligang; Liu, Shaotong; Liu, Chunze Energy & Fuels, Vol. 31, Issue 11 https://doi.org/10.1021/acs.energyfuels.7b02322	journal	October 2017
Ru and Ru–Ni Nanoparticles on TiO ₂ Support as Extremely Active Catalysts for Hydrogen Production from Ammonia–Borane Mori, Kohsuke; Miyawaki, Kohei; Yamashita, Hiromi ACS Catalysis, Vol. 6, Issue 5 https://doi.org/10.1021/acscatal.6b00715	journal	April 2016
Organic Chemical Reactions in Supercritical Water Savage, Phillip E. Chemical Reviews, Vol. 99, Issue 2 https://doi.org/10.1021/cr9700989	journal	February 1999
Direct Access to Oxidation-Resistant Nickel Catalysts through an Organometallic Precursor Costa, Natália J. S.; Jardim, Renato F.; Masunaga, Sueli H. ACS Catalysis, Vol. 2, Issue 6 https://doi.org/10.1021/cs200609e	journal	April 2012
Aqueous high-temperature chemistry of carbo- and heterocycles. 19. Pyrroles and indoles Katritzky, Alan R.; Luxem, Franz J.; Murugan, Ramiah Energy & Fuels, Vol. 6, Issue 4 https://doi.org/10.1021/ef00034a014	journal	July 1992
Aqueous High-Temperature Chemistry of Carbo- and Heterocycles. 23.Reactions of Pyridine Analogs and Benzopyrroles in Supercritical Water at 460 .degree.C Katritzky, Alan R.; Barcock, Richard A.; Siskin, Michael Energy & Fuels, Vol. 8, Issue 4 https://doi.org/10.1021/ef00046a026	journal	July 1994
Aqueous High-Temperature Chemistry. 24. Nitrogen-Containing Heterocycles in Supercritical Water at 460 .degree.C Katritzky, Alan R.; Shipkova, Petia A.; Allin, Steven M. Energy & Fuels, Vol. 9, Issue 4 https://doi.org/10.1021/ef00052a003	journal	July 1995
Hydrothermal Liquefaction and Gasification of Nannochloropsis sp. Brown, Tylisha M.; Duan, Peigao; Savage, Phillip E. Energy & Fuels, Vol. 24, Issue 6 https://doi.org/10.1021/ef100203u	journal	June 2010
Chemical processing in high-pressure aqueous environments. 2. Development of catalysts for gasification Elliott, Douglas C.; Sealock, L. John; Baker, Eddie G. Industrial & Engineering Chemistry Research, Vol. 32, Issue 8 https://doi.org/10.1021/ie00020a002	journal	August 1993
Valence State Study of Supported Ruthenium Ru/MgO Catalysts Larichev, Yurii V. The Journal of Physical Chemistry C, Vol. 112, Issue 38 https://doi.org/10.1021/jp803742g	journal	August 2008
Ru–Ni/Al ₂ O ₃ bimetallic catalysts with high catalytic activity for N -propylcarbazole hydrogenation Li, Chenguang; Yang, Ming; Liu, Zhenjie Catalysis Science & Technology, Vol. 10, Issue 7 https://doi.org/10.1039/C9CY02528F	journal	January 2020
Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points Henkelman, Graeme; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22 https://doi.org/10.1063/1.1323224	journal	December 2000
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Special points for Brillouin-zone integrations Monkhorst, Hendrik J.; Pack, James D. Physical Review B, Vol. 13, Issue 12, p. 5188-5192 https://doi.org/10.1103/PhysRevB.13.5188	journal	June 1976
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)] Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 78, Issue 7 https://doi.org/10.1103/PhysRevLett.78.1396	journal	February 1997
Raney Ni-Sn Catalyst for H2 Production from Biomass-Derived Hydrocarbons Huber, G. W. Science, Vol. 300, Issue 5628 https://doi.org/10.1126/science.1085597	journal	June 2003

Similar Records

Hydrodenitrogenation of indole over NiMo sulfide catalysts

Conference · Mon Dec 30 23:00:00 EST 1996 · OSTI ID:468034

Catalytic hydrodeoxygenation. III. Interactions between catalytic hydrodeoxygenation of m-cresol and hydrodenitrogenation of indole

Journal Article · Mon Feb 28 23:00:00 EST 1983 · J. Catal.; (United States) · OSTI ID:5237549

Preliminary thermodynamic studies on the hydrodenitrogenation of indole

Technical Report · Wed Nov 30 23:00:00 EST 1988 · OSTI ID:6632324

Related Subjects

42 ENGINEERING
bimetallic
density functional theory
hydrothermal
indole
kinetics

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

Citation Formats

References (40)

Similar Records

Related Subjects