skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Dissecting the Performance of Nanoporous Gold Catalysts for Oxygen-Assisted Coupling of Methanol with Fundamental Mechanistic and Kinetic Information

Abstract

The utility of the surface reactivity observed for model systems under ultrahigh vacuum for predicting the performance of catalytic materials under ambient flow conditions is a highly debated topic in heterogeneous catalysis. Herein we show that vast differences in selectivity observed for methanol self-coupling across wide ranges of temperature and reactant pressure can be accurately predicted utilizing the kinetics and mechanism obtained from model studies on gold single crystals in ultrahigh vacuum regressed to fit transient pulse responses over nanoporous gold (Ag 0.03Au 0.97) at low pressures. Specifically, microkinetic modeling of the complex sequence of elementary steps governing this reaction predicts the dramatic effect of reactant partial pressure on the product distribution and leads to conclusion that the gas phase partial pressures of both reactants and the reaction temperature determine the changes in selectivity to methyl formate formation. Moreover, thorough analysis of the reaction network indicates that the product distribution becomes increasingly insensitive to kinetic effects at pressures approaching 1 bar, leading toward 100% selectivity methyl formate. A rigorous kinetic sensitivity analysis also demonstrates the complex interplay of the kinetics of the elementary steps and the overall catalytic behavior.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1]
  1. Harvard Univ., Cambridge, MA (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC); Harvard Univ., Cambridge, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1566571
Grant/Contract Number:  
SC0012573
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 9; Journal Issue: 5; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (heterogeneous); mesostructured materials; materials and chemistry by design; synthesis (novel materials)

Citation Formats

Reece, Christian, Luneau, Mathilde, and Madix, Robert J. Dissecting the Performance of Nanoporous Gold Catalysts for Oxygen-Assisted Coupling of Methanol with Fundamental Mechanistic and Kinetic Information. United States: N. p., 2019. Web. doi:10.1021/acscatal.9b00664.
Reece, Christian, Luneau, Mathilde, & Madix, Robert J. Dissecting the Performance of Nanoporous Gold Catalysts for Oxygen-Assisted Coupling of Methanol with Fundamental Mechanistic and Kinetic Information. United States. doi:10.1021/acscatal.9b00664.
Reece, Christian, Luneau, Mathilde, and Madix, Robert J. Tue . "Dissecting the Performance of Nanoporous Gold Catalysts for Oxygen-Assisted Coupling of Methanol with Fundamental Mechanistic and Kinetic Information". United States. doi:10.1021/acscatal.9b00664. https://www.osti.gov/servlets/purl/1566571.
@article{osti_1566571,
title = {Dissecting the Performance of Nanoporous Gold Catalysts for Oxygen-Assisted Coupling of Methanol with Fundamental Mechanistic and Kinetic Information},
author = {Reece, Christian and Luneau, Mathilde and Madix, Robert J.},
abstractNote = {The utility of the surface reactivity observed for model systems under ultrahigh vacuum for predicting the performance of catalytic materials under ambient flow conditions is a highly debated topic in heterogeneous catalysis. Herein we show that vast differences in selectivity observed for methanol self-coupling across wide ranges of temperature and reactant pressure can be accurately predicted utilizing the kinetics and mechanism obtained from model studies on gold single crystals in ultrahigh vacuum regressed to fit transient pulse responses over nanoporous gold (Ag0.03Au0.97) at low pressures. Specifically, microkinetic modeling of the complex sequence of elementary steps governing this reaction predicts the dramatic effect of reactant partial pressure on the product distribution and leads to conclusion that the gas phase partial pressures of both reactants and the reaction temperature determine the changes in selectivity to methyl formate formation. Moreover, thorough analysis of the reaction network indicates that the product distribution becomes increasingly insensitive to kinetic effects at pressures approaching 1 bar, leading toward 100% selectivity methyl formate. A rigorous kinetic sensitivity analysis also demonstrates the complex interplay of the kinetics of the elementary steps and the overall catalytic behavior.},
doi = {10.1021/acscatal.9b00664},
journal = {ACS Catalysis},
issn = {2155-5435},
number = 5,
volume = 9,
place = {United States},
year = {2019},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Save / Share: