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Title: Changing the Mechanism for CO 2 Hydrogenation Using Solvent-Dependent Thermodynamics

Abstract

A critical scientific challenge for utilization of CO2 is the development of catalyst systems that do not depend upon expensive or environmentally unfriendly reagents, such as precious metals, strong organic bases, and organic solvents. We have used thermodynamic insights to predict and demonstrate that the HCoI(dmpe)2 catalyst system, previously described for use in organic solvents, can hydrogenate CO2 to formate in water with bicarbonate as the only added reagent. Replacing tetrahydrofuran as the solvent with water changes the mechanism for catalysis by altering the thermodynamics for hydride transfer to CO2 from a key dihydride intermediate. The need for a strong organic base was eliminated by performing catalysis in water due to the change in mechanism. These studies demonstrate that the solvent plays a pivotal role in determining the reaction thermodynamics and thereby catalytic mechanism and activity. The research was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Catalysis Science Group, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1411891
Report Number(s):
PNNL-SA-128948
Journal ID: ISSN 1433-7851; KC0302010
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Volume: 56; Journal Issue: 47; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; carbon dioxide; solvent effects; hydrogen; catalysis; cobalt; thermodynamics

Citation Formats

Burgess, Samantha A., Appel, Aaron M., Linehan, John C., and Wiedner, Eric S. Changing the Mechanism for CO 2 Hydrogenation Using Solvent-Dependent Thermodynamics. United States: N. p., 2017. Web. doi:10.1002/anie.201709319.
Burgess, Samantha A., Appel, Aaron M., Linehan, John C., & Wiedner, Eric S. Changing the Mechanism for CO 2 Hydrogenation Using Solvent-Dependent Thermodynamics. United States. doi:10.1002/anie.201709319.
Burgess, Samantha A., Appel, Aaron M., Linehan, John C., and Wiedner, Eric S. Mon . "Changing the Mechanism for CO 2 Hydrogenation Using Solvent-Dependent Thermodynamics". United States. doi:10.1002/anie.201709319.
@article{osti_1411891,
title = {Changing the Mechanism for CO 2 Hydrogenation Using Solvent-Dependent Thermodynamics},
author = {Burgess, Samantha A. and Appel, Aaron M. and Linehan, John C. and Wiedner, Eric S.},
abstractNote = {A critical scientific challenge for utilization of CO2 is the development of catalyst systems that do not depend upon expensive or environmentally unfriendly reagents, such as precious metals, strong organic bases, and organic solvents. We have used thermodynamic insights to predict and demonstrate that the HCoI(dmpe)2 catalyst system, previously described for use in organic solvents, can hydrogenate CO2 to formate in water with bicarbonate as the only added reagent. Replacing tetrahydrofuran as the solvent with water changes the mechanism for catalysis by altering the thermodynamics for hydride transfer to CO2 from a key dihydride intermediate. The need for a strong organic base was eliminated by performing catalysis in water due to the change in mechanism. These studies demonstrate that the solvent plays a pivotal role in determining the reaction thermodynamics and thereby catalytic mechanism and activity. The research was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.},
doi = {10.1002/anie.201709319},
journal = {Angewandte Chemie (International Edition)},
issn = {1433-7851},
number = 47,
volume = 56,
place = {United States},
year = {2017},
month = {10}
}

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