DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: In-situ evaluation for upgrading of biomass over noble metal catalysts by isotopic tracing and NMR monitoring

Journal Article · · Journal of Analytical and Applied Pyrolysis
 [1];  [1];  [2];  [2]; ORCiD logo [3]
  1. Southeast Univ., Nanjing (China); Key Lab. of Energy Thermal Conversion and Control of Ministry of Education, Nanjing (China)
  2. Qingdao Univ. (China); Lab. of New Fiber Materials and Modern Textile, Qingdao (China)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)

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.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1515639
Journal Information:
Journal of Analytical and Applied Pyrolysis, Vol. 137, Issue C; ISSN 0165-2370
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 6 works
Citation information provided by
Web of Science

References (30)

The Path Forward for Biofuels and Biomaterials journal January 2006
Techno-economic comparison of biomass-to-transportation fuels via pyrolysis, gasification, and biochemical pathways journal November 2010
In situ infrared spectroscopy applied to catalytic reactions on metal single crystals journal October 2001
The effect of metal–acid balance in Pt-loading dealuminated Y zeolite catalysts on the hydrogenation of benzene journal August 1999
Interaction of D(H) atoms with physisorbed benzene and (1,4)‐dimethyl‐cyclohexane: Hydrogenation and H abstraction journal February 1996
Ab Initio Reaction Path Analysis of Benzene Hydrogenation to Cyclohexane on Pt(111) journal February 2005
Cyclohexane Ring Opening on Alumina-Supported Rh and Ir Nanoparticles journal March 2007
Hydroconversion of cyclohexene using catalysts containing Pt, Pd, Ir and Re supported on H-ZSM-5 zeolite journal April 2005
Characterization and Evaluation of Methylcyclopentane and Cyclohexane Ring Opening over Ir/ZrO2–MoO3 Catalysts journal April 2008
Cyclohexane conversion over H-zeolite supported platinum journal April 2002
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
Ring opening of methylcyclopentane on alumina-supported Rh catalysts of different metal loadings journal June 2000
The Effect of Hydrogen Partial-Pressure on Methylcyclopentane Ring-Opening journal February 1995
Selective ring-opening of methylcyclopentane on platinum-based bimetallic catalysts journal November 2009
Reaction Mechanism of Methylcyclopentane Ring Opening over a Bifunctional Pt-Al 2 O 3 Catalyst journal December 1978
Catalytic Ring Opening of MCH and MCP Over Ir Containing USY and HZSM-5 with the Same SiO2/Al2O3 Ratio journal April 2012
Reactions of methylcyclopentane on Rh–Pt catalyst prepared by underpotential deposition of Rh on Pt/SiO2 journal September 2007
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
Tuning the selectivity for ring-opening reactions of methylcyclopentane over Pt catalysts: A mechanistic study from first-principles calculations journal January 2012
Ring-Opening Reactions of Methylcyclopentane over Metal Catalysts, M = Pt, Rh, Ir, and Pd: A Mechanistic Study from First-Principles Calculations journal January 2013
Hydrodeoxygenation by deuterium gas – a powerful way to provide insight into the reaction mechanisms journal January 2013
Hydrocarbon adsorption on rhodium: a search for reactive intermediates journal September 1987
Reactions of methylcyclopentane over supported-metal catalysts journal January 1992
The kinetics of H/D exchange in cyclopentane journal February 2003
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
Density Functionals with Broad Applicability in Chemistry journal February 2008
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
Determination of Gas Concentrations in Liquids by Nuclear Magnetic Resonance: Hydrogen in Organic Solvents journal April 2012
Direct NMR Evidence for the Presence of Mobile Surface Hydrides on Ruthenium Nanoparticles journal April 2005
Comparative NMR Properties of H 2 and HD in Toluene- d 8 and in H 2 /HD@C 60 journal November 2010

Cited By (1)

In-depth study on the effect of oxygen-containing functional groups in pyrolysis oil by P-31 NMR journal January 2019