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Title: Molecular-scale Understanding of Selective Oxidative Transformations of Alcohols Promoted by Au and Au-based Alloys

Technical Report ·
DOI:https://doi.org/10.2172/1515177· OSTI ID:1515177
 [1];  [2];  [2];  [2];  [2];  [2];  [2];  [2];  [2];  [2]
  1. Harvard Univ., Cambridge, MA (United States). School of Engineering and Applied Sciences (SEAS)
  2. Harvard Univ., Cambridge, MA (United States)

This project developed a molecular-scale mechanistic framework for complex selective oxidation of alcohols and amines on O-covered Au and Ag-Au alloys that guides the design of selective and energy efficient processes. Our work has led to the discovery of new classes of reactions. We have also bridged a wide range of pressures and materials complexity by demonstrating catalytic activity using nanoporous Au catalysts. The selective oxidation of alcohols with each other and with other reactants, such as CO or amines, were focused on in this work because it is a key technology for large-scale chemical synthesis. Theory and experiment were combined to understand selective oxidation reactions on Au. Significant accomplishments are: (i) development of molecular-scale mechanisms for selective alcohol oxidation over Au surfaces; (ii) discovery of two new classes of reactions on O/Au—amide synthesis from amines and aldehydes and carbonylation of alcohols; and, (iii) demonstration that the mechanisms derived from our fundamental work predict the conditions for efficient catalysis using nanoporous Au catalysts under flow conditions at atmospheric pressure. This work has made an unprecedented connection between fundamental surface science studies and their implementation under catalytic conditions. This research fits squarely in the DOE-BES mission articulated in several BES Basic Research Needs (BRN) reports. “Catalysis for Energy” emphasizes the need to fabricate, design, characterize, and assemble new structures, including nanoscale alloys, and to understand and model their chemical behavior for energy-related applications. Our studies of nanoporous materials also exploit unique mesoscale phenomena to address complex energy-related issues (http://www.meso2012.com/).

Research Organization:
Harvard Univ., Cambridge, MA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
DOE Contract Number:
FG02-84ER13289
OSTI ID:
1515177
Report Number(s):
Final
Country of Publication:
United States
Language:
English

References (7)

van der Waals Interactions Determine Selectivity in Catalysis by Metallic Gold journal September 2014
Switching Selectivity in Oxidation Reactions on Gold: The Mechanism of C–C vs C–H Bond Activation in the Acetate Intermediate on Au(111) journal August 2014
Alkyl groups as synthetic vehicles in gold-mediated oxidative coupling reactions journal January 2013
Ag/Au Mixed Sites Promote Oxidative Coupling of Methanol on the Alloy Surface journal March 2014
Tuning the Stability of Surface Intermediates Using Adsorbed Oxygen: Acetate on Au(111)
  • Cremer, Till; Siler, Cassandra G. F.; Rodríguez-Reyes, Juan Carlos F.
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 7 https://doi.org/10.1021/jz500192k
journal March 2014
Selective Activation of Methyl C–H Bonds of Toluene by Oxygen on Metallic Gold journal May 2018
Methyl ester synthesis catalyzed by nanoporous gold: from 10 −9 Torr to 1 atm journal January 2015

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