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Title: CO 2 Hydrogenation Catalysts with Deprotonated Picolinamide Ligands

Abstract

In an effort to design concepts for highly active catalysts for the hydrogenation of CO 2 to formate in basic water, we have prepared in this paper several catalysts with picolinic acid, picolinamide, and its derivatives, and we investigated their catalytic activity. The CO 2 hydrogenation catalyst having a 4-hydroxy-N-methylpicolinamidate ligand exhibited excellent activity even under ambient conditions (0.1 MPa, 25 °C) in basic water, exhibiting a TON of 14700, a TOF of 167 h –1, and producing a 0.64 M formate concentration. Finally, its high catalytic activity originates from strong electron donation by the anionic amide moiety in addition to the phenolic O functionality.

Authors:
 [1]; ORCiD logo [1];  [2];  [3];  [3]; ORCiD logo [3]; ORCiD logo [1]
  1. Research Institute of Energy Frontier, Department of Energy and Environment, National Institute of Advanced Industrial Science and Technology, Tsukuba Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan
  2. Department of Natural Science, Baruch College, CUNY, New York, New York 10010-5585, United States
  3. Chemistry Division, Brookhaven National Laboratory, Upton, New York 11973-5000, United States
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States); National Inst. of Advanced Industrial Science and Technology (AIST), Tsukuba (Japan)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Japan Science and Technology Agency (JST); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1377083
Alternate Identifier(s):
OSTI ID: 1395940; OSTI ID: 1507720
Report Number(s):
BNL-114356-2017-JA
Journal ID: ISSN 2155-5435
Grant/Contract Number:  
SC0012704; JPMJCR12Z0
Resource Type:
Published Article
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Name: ACS Catalysis; 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; CO2 hydrogenation; deprotonated picolinamide ligand; DFT calculations; formate production; hydrogen storage; water-soluble Ir catalysts

Citation Formats

Kanega, Ryoichi, Onishi, Naoya, Szalda, David J., Ertem, Mehmed Z., Muckerman, James T., Fujita, Etsuko, and Himeda, Yuichiro. CO2 Hydrogenation Catalysts with Deprotonated Picolinamide Ligands. United States: N. p., 2017. Web. doi:10.1021/acscatal.7b02280.
Kanega, Ryoichi, Onishi, Naoya, Szalda, David J., Ertem, Mehmed Z., Muckerman, James T., Fujita, Etsuko, & Himeda, Yuichiro. CO2 Hydrogenation Catalysts with Deprotonated Picolinamide Ligands. United States. doi:10.1021/acscatal.7b02280.
Kanega, Ryoichi, Onishi, Naoya, Szalda, David J., Ertem, Mehmed Z., Muckerman, James T., Fujita, Etsuko, and Himeda, Yuichiro. Fri . "CO2 Hydrogenation Catalysts with Deprotonated Picolinamide Ligands". United States. doi:10.1021/acscatal.7b02280.
@article{osti_1377083,
title = {CO2 Hydrogenation Catalysts with Deprotonated Picolinamide Ligands},
author = {Kanega, Ryoichi and Onishi, Naoya and Szalda, David J. and Ertem, Mehmed Z. and Muckerman, James T. and Fujita, Etsuko and Himeda, Yuichiro},
abstractNote = {In an effort to design concepts for highly active catalysts for the hydrogenation of CO2 to formate in basic water, we have prepared in this paper several catalysts with picolinic acid, picolinamide, and its derivatives, and we investigated their catalytic activity. The CO2 hydrogenation catalyst having a 4-hydroxy-N-methylpicolinamidate ligand exhibited excellent activity even under ambient conditions (0.1 MPa, 25 °C) in basic water, exhibiting a TON of 14700, a TOF of 167 h–1, and producing a 0.64 M formate concentration. Finally, its high catalytic activity originates from strong electron donation by the anionic amide moiety in addition to the phenolic O– functionality.},
doi = {10.1021/acscatal.7b02280},
journal = {ACS Catalysis},
number = ,
volume = ,
place = {United States},
year = {2017},
month = {8}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1021/acscatal.7b02280

Citation Metrics:
Cited by: 12 works
Citation information provided by
Web of Science

Figures / Tables:

Scheme 1 Scheme 1: Mononuclear Catalysts for Selective CO2 Hydrogenation to Generate Formate under Ambient Conditions in Basic Water (pH ∼ 8.2)

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Works referencing / citing this record:

Hydrogenation of CO 2 to Formate with H 2 : Transition Metal Free Catalyst Based on a Lewis Pair
journal, November 2018

  • Zhao, Tianxiang; Hu, Xingbang; Wu, Youting
  • Angewandte Chemie International Edition, Vol. 58, Issue 3
  • DOI: 10.1002/anie.201809634

Iridium–NHC-based catalyst for ambient pressure storage and low temperature release of H 2 via the CO 2 /HCO 2 H couple
journal, January 2018

  • Semwal, Shrivats; Kumar, Abhishek; Choudhury, Joyanta
  • Catalysis Science & Technology, Vol. 8, Issue 23
  • DOI: 10.1039/c8cy02069h

Hydrogenation of CO 2 to Formate with H 2 : Transition Metal Free Catalyst Based on a Lewis Pair
journal, November 2018

  • Zhao, Tianxiang; Hu, Xingbang; Wu, Youting
  • Angewandte Chemie International Edition, Vol. 58, Issue 3
  • DOI: 10.1002/anie.201809634

Iridium–NHC-based catalyst for ambient pressure storage and low temperature release of H 2 via the CO 2 /HCO 2 H couple
journal, January 2018

  • Semwal, Shrivats; Kumar, Abhishek; Choudhury, Joyanta
  • Catalysis Science & Technology, Vol. 8, Issue 23
  • DOI: 10.1039/c8cy02069h

    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.