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

Abstract

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 Basicmore » 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/).« less

Authors:
 [1]
  1. Harvard Univ., Cambridge, MA (United States)
Publication Date:
Research Org.:
Harvard University
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1515177
Report Number(s):
Final
DOE Contract Number:  
FG02-84ER13289
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Catalysis, surface chemistry, chemical synthesis

Citation Formats

Friend, Cynthia. Molecular-scale Understanding of Selective Oxidative Transformations of Alcohols Promoted by Au and Au-based Alloys. United States: N. p., 2018. Web. doi:10.2172/1515177.
Friend, Cynthia. Molecular-scale Understanding of Selective Oxidative Transformations of Alcohols Promoted by Au and Au-based Alloys. United States. doi:10.2172/1515177.
Friend, Cynthia. Fri . "Molecular-scale Understanding of Selective Oxidative Transformations of Alcohols Promoted by Au and Au-based Alloys". United States. doi:10.2172/1515177. https://www.osti.gov/servlets/purl/1515177.
@article{osti_1515177,
title = {Molecular-scale Understanding of Selective Oxidative Transformations of Alcohols Promoted by Au and Au-based Alloys},
author = {Friend, Cynthia},
abstractNote = {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/).},
doi = {10.2172/1515177},
journal = {},
number = ,
volume = ,
place = {United States},
year = {2018},
month = {9}
}