In-situ evaluation for upgrading of biomass over noble metal catalysts by isotopic tracing and NMR monitoring
Abstract
One of the key challenges in studying the upgrading processes for the conversion of biomass is developing an understanding of the underlying conversion mechanism at the atomic scale. This study proposed an innovative high pressure in situ NMR monitoring approach for an isotopic traced upgrading process, which demonstrated a powerful capability to identify key products and provide insights into the reaction structure. The investigations for ring opening of two basic model compounds – methylcyclopentane (MCP) and cyclohexane (CH) on Ir, Pt, Ru and Pd/γ-Al2O3 at 55 and 110 °C have been accomplished. For the study performed at 110 °C on Ir, Pt and Ru catalysts, the trend of H/D exchange rates were clearly dependent on the position on the ring with the highest exchange rate for the unhindered (or open side) and the lowest rate with the methyl group. However, Pd could perform almost equally efficient H/D exchanges for all sides, which may indicate that the “turnover” reactions could also occur on Pd. For both MCP and CH, Ru performed the most efficient H/D exchanges (C–H bond activation), and ring opened products were only observed with the Ru catalyst at 110 °C suggesting it is the most promising ring openingmore »
- Authors:
-
[3]
- Southeast Univ., Nanjing (China); Key Lab. of Energy Thermal Conversion and Control of Ministry of Education, Nanjing (China)
- Qingdao Univ. (China); Lab. of New Fiber Materials and Modern Textile, Qingdao (China)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1515639
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Analytical and Applied Pyrolysis
- Additional Journal Information:
- Journal Volume: 137; Journal Issue: C; Journal ID: ISSN 0165-2370
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Ben, Haoxi, Wu, Zhihong, Han, Guangting, Jiang, Wei, and Ragauskas, Arthur J. In-situ evaluation for upgrading of biomass over noble metal catalysts by isotopic tracing and NMR monitoring. United States: N. p., 2018.
Web. doi:10.1016/j.jaap.2018.12.008.
Ben, Haoxi, Wu, Zhihong, Han, Guangting, Jiang, Wei, & Ragauskas, Arthur J. In-situ evaluation for upgrading of biomass over noble metal catalysts by isotopic tracing and NMR monitoring. United States. https://doi.org/10.1016/j.jaap.2018.12.008
Ben, Haoxi, Wu, Zhihong, Han, Guangting, Jiang, Wei, and Ragauskas, Arthur J. Tue .
"In-situ evaluation for upgrading of biomass over noble metal catalysts by isotopic tracing and NMR monitoring". United States. https://doi.org/10.1016/j.jaap.2018.12.008. https://www.osti.gov/servlets/purl/1515639.
@article{osti_1515639,
title = {In-situ evaluation for upgrading of biomass over noble metal catalysts by isotopic tracing and NMR monitoring},
author = {Ben, Haoxi and Wu, Zhihong and Han, Guangting and Jiang, Wei and Ragauskas, Arthur J.},
abstractNote = {One of the key challenges in studying the upgrading processes for the conversion of biomass is developing an understanding of the underlying conversion mechanism at the atomic scale. This study proposed an innovative high pressure in situ NMR monitoring approach for an isotopic traced upgrading process, which demonstrated a powerful capability to identify key products and provide insights into the reaction structure. The investigations for ring opening of two basic model compounds – methylcyclopentane (MCP) and cyclohexane (CH) on Ir, Pt, Ru and Pd/γ-Al2O3 at 55 and 110 °C have been accomplished. For the study performed at 110 °C on Ir, Pt and Ru catalysts, the trend of H/D exchange rates were clearly dependent on the position on the ring with the highest exchange rate for the unhindered (or open side) and the lowest rate with the methyl group. However, Pd could perform almost equally efficient H/D exchanges for all sides, which may indicate that the “turnover” reactions could also occur on Pd. For both MCP and CH, Ru performed the most efficient H/D exchanges (C–H bond activation), and ring opened products were only observed with the Ru catalyst at 110 °C suggesting it is the most promising ring opening catalyst.},
doi = {10.1016/j.jaap.2018.12.008},
journal = {Journal of Analytical and Applied Pyrolysis},
number = C,
volume = 137,
place = {United States},
year = {2018},
month = {12}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 3 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
The Path Forward for Biofuels and Biomaterials
journal, January 2006
- Ragauskas, Arthur J.; Williams, Charlotte K.; Davison, Brian H.
- Science, Vol. 311, Issue 5760, p. 484-489
Techno-economic comparison of biomass-to-transportation fuels via pyrolysis, gasification, and biochemical pathways
journal, November 2010
- Anex, Robert P.; Aden, Andy; Kazi, Feroz Kabir
- Fuel, Vol. 89, p. S29-S35
In situ infrared spectroscopy applied to catalytic reactions on metal single crystals
journal, October 2001
- Shorthouse, L. J.; Jugnet, Y.; Bertolini, J. C.
- Catalysis Today, Vol. 70, Issue 1-3
The effect of metalâacid balance in Pt-loading dealuminated Y zeolite catalysts on the hydrogenation of benzene
journal, August 1999
- Wang, J.
- Applied Catalysis A: General, Vol. 184, Issue 2
Interaction of D(H) atoms with physisorbed benzene and (1,4)‐dimethyl‐cyclohexane: Hydrogenation and H abstraction
journal, February 1996
- Lutterloh, C.; Biener, J.; Schenk, A.
- The Journal of Chemical Physics, Vol. 104, Issue 6
Ab Initio Reaction Path Analysis of Benzene Hydrogenation to Cyclohexane on Pt(111) †
journal, February 2005
- Saeys, Mark; Reyniers, M. -F.; Neurock, M.
- The Journal of Physical Chemistry B, Vol. 109, Issue 6
Cyclohexane Ring Opening on Alumina-Supported Rh and Ir Nanoparticles
journal, March 2007
- Rodríguez-Gattorno, Geonel; Alemán-Vázquez, Laura O.; Angeles-Franco, Xochitl
- Energy & Fuels, Vol. 21, Issue 2
Hydroconversion of cyclohexene using catalysts containing Pt, Pd, Ir and Re supported on H-ZSM-5 zeolite
journal, April 2005
- Aboul-Gheit, Ahmed K.; Aboul-Fotouh, Sameh M.; Aboul-Gheit, Noha A. K.
- Applied Catalysis A: General, Vol. 283, Issue 1-2
Characterization and Evaluation of Methylcyclopentane and Cyclohexane Ring Opening over Ir/ZrO2–MoO3 Catalysts
journal, April 2008
- Wang, Zhenhui; Nelson, Alan E.
- Catalysis Letters, Vol. 123, Issue 3-4
Cyclohexane conversion over H-zeolite supported platinum
journal, April 2002
- Onyestyák, Gy.; Pál-Borbély, G.; Beyer, H. K.
- Applied Catalysis A: General, Vol. 229, Issue 1-2
Trapping-Mediated Dissociative Chemisorption of Cycloalkanes on Ru(001) and Ir(111): Influence of Ring Strain and Molecular Geometry on the Activation of C−C and C−H Bonds
journal, February 2001
- Hagedorn, Christopher J.; Weiss, Michael J.; Kim, Tae Won
- Journal of the American Chemical Society, Vol. 123, Issue 5
Ring opening of methylcyclopentane on alumina-supported Rh catalysts of different metal loadings
journal, June 2000
- Teschner, D.; Matusek, K.; Paal, Z.
- Journal of Catalysis, Vol. 192, Issue 2
The Effect of Hydrogen Partial-Pressure on Methylcyclopentane Ring-Opening
journal, February 1995
- Vaarkamp, M.; Dijkstra, P.; Vangrondelle, J.
- Journal of Catalysis, Vol. 151, Issue 2
Selective ring-opening of methylcyclopentane on platinum-based bimetallic catalysts
journal, November 2009
- Samoila, P.; Boutzeloit, M.; Especel, C.
- Applied Catalysis A: General, Vol. 369, Issue 1-2
Reaction Mechanism of Methylcyclopentane Ring Opening over a Bifunctional Pt-Al 2 O 3 Catalyst
journal, December 1978
- Christoffel, Erhard G.; Röbschläger, Karl-H.
- Industrial & Engineering Chemistry Product Research and Development, Vol. 17, Issue 4
Catalytic Ring Opening of MCH and MCP Over Ir Containing USY and HZSM-5 with the Same SiO2/Al2O3 Ratio
journal, April 2012
- Upare, Dipali P.; Yoon, Songhun; Lee, Chul Wee
- Catalysis Letters, Vol. 142, Issue 6
Reactions of methylcyclopentane on Rh–Pt catalyst prepared by underpotential deposition of Rh on Pt/SiO2
journal, September 2007
- Győrffy, Nóra; Wootsch, Attila; Szabó, Sándor
- Topics in Catalysis, Vol. 46, Issue 1-2
Selective ring opening of methylcyclopentane over Pt/γ-Al2O3, Ir/γ-Al2O3 and Pt-Ir/γ-Al2O3 catalysts with hydrogen at atmospheric pressure
journal, January 2012
- Djeddi, Amel; Fechete, Ioana; Garin, François
- Applied Catalysis A: General, Vol. 413-414
Tuning the selectivity for ring-opening reactions of methylcyclopentane over Pt catalysts: A mechanistic study from first-principles calculations
journal, January 2012
- Zhao, Zhi-Jian; Moskaleva, Lyudmila V.; Rösch, Notker
- Journal of Catalysis, Vol. 285, Issue 1
Ring-Opening Reactions of Methylcyclopentane over Metal Catalysts, M = Pt, Rh, Ir, and Pd: A Mechanistic Study from First-Principles Calculations
journal, January 2013
- Zhao, Zhi-Jian; Moskaleva, Lyudmila V.; Rösch, Notker
- ACS Catalysis, Vol. 3, Issue 2
Hydrodeoxygenation by deuterium gas – a powerful way to provide insight into the reaction mechanisms
journal, January 2013
- Ben, Haoxi; Ferguson, Glen A.; Mu, Wei
- Physical Chemistry Chemical Physics, Vol. 15, Issue 44
Hydrocarbon adsorption on rhodium: a search for reactive intermediates
journal, September 1987
- Cogen, Jeffrey M.; Maier, Wilhelm F.
- Langmuir, Vol. 3, Issue 5
Reactions of methylcyclopentane over supported-metal catalysts
journal, January 1992
- Brown, Ronald; Dolan, Anne S.; Kemball, Charles
- Journal of the Chemical Society, Faraday Transactions, Vol. 88, Issue 16
The kinetics of H/D exchange in cyclopentane
journal, February 2003
- Oudenhuijzen, M.
- Journal of Catalysis, Vol. 214, Issue 1
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals
journal, July 2007
- Zhao, Yan; Truhlar, Donald G.
- Theoretical Chemistry Accounts, Vol. 120, Issue 1-3
Density Functionals with Broad Applicability in Chemistry
journal, February 2008
- Zhao, Yan; Truhlar, Donald G.
- Accounts of Chemical Research, Vol. 41, Issue 2
Mechanisticin situ High-Pressure NMR Studies of Benzene Hydrogenation by Supramolecular Cluster Catalysis with [(η6-C6H6)(η6-C6Me6)2Ru3(μ3-O)(μ2-OH)(μ2-H)2][BF4]
journal, December 2002
- Laurenczy, Gabor; Faure, Matthieu; Vieille-Petit, Ludovic
- Advanced Synthesis & Catalysis, Vol. 344, Issue 10
Determination of Gas Concentrations in Liquids by Nuclear Magnetic Resonance: Hydrogen in Organic Solvents
journal, April 2012
- Krüger, Mario Baseda; Selle, Carmen; Heller, Detlef
- Journal of Chemical & Engineering Data, Vol. 57, Issue 6
Direct NMR Evidence for the Presence of Mobile Surface Hydrides on Ruthenium Nanoparticles
journal, April 2005
- Pery, Tal; Pelzer, Katrin; Buntkowsky, Gerd
- ChemPhysChem, Vol. 6, Issue 4
Comparative NMR Properties of H 2 and HD in Toluene- d 8 and in H 2 /HD@C 60 †
journal, November 2010
- Chen, Judy Y. -C.; Martí, Angel A.; Turro, Nicholas J.
- The Journal of Physical Chemistry B, Vol. 114, Issue 45
Works referencing / citing this record:
In-depth study on the effect of oxygen-containing functional groups in pyrolysis oil by P-31 NMR
journal, January 2019
- Wu, Zhihong; Ben, Haoxi; Yang, Yunyi
- RSC Advances, Vol. 9, Issue 47