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Title: CO2 Hydrogenation Catalysts with Deprotonated Picolinamide Ligands

Journal Article · · ACS Catalysis
 [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
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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.

Research Organization:
Brookhaven National Lab. (BNL), Upton, NY (United States); National Inst. of Advanced Industrial Science and Technology (AIST), Tsukuba (Japan)
Sponsoring Organization:
Japan Science and Technology Agency (JST); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
Grant/Contract Number:
SC0012704; JPMJCR12Z0
OSTI ID:
1377083
Alternate ID(s):
OSTI ID: 1395940; OSTI ID: 1507720
Report Number(s):
BNL-114356-2017-JA
Journal Information:
ACS Catalysis, Journal Name: ACS Catalysis; ISSN 2155-5435
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 54 works
Citation information provided by
Web of Science

References (37)

A series of tricarbonylrhenium(I) complexes with the N-methyl-2-pyridinecarboxyamide ligand: Synthesis, structure, spectroscopic characterization and computational studies journal February 2015
A Viable Hydrogen-Storage System Based On Selective Formic Acid Decomposition with a Ruthenium Catalyst journal May 2008
Density Functionals with Broad Applicability in Chemistry journal February 2008
Iron catalyzed CO 2 hydrogenation to formate enhanced by Lewis acid co-catalysts journal January 2015
Photocatalytic reduction of CO2 using metal complexes journal December 2015
The irreversible momentum of clean energy journal January 2017
Efficient Hydrogen Storage and Production Using a Catalyst with an Imidazoline‐Based, Proton‐Responsive Ligand journal December 2016
Interconversion between Formic Acid and H2/CO2 using Rhodium and Ruthenium Catalysts for CO2 Fixation and H2 Storage journal January 2011
A Cobalt-Based Catalyst for the Hydrogenation of CO 2 under Ambient Conditions journal July 2013
Mechanistic Insight through Factors Controlling Effective Hydrogenation of CO 2 Catalyzed by Bioinspired Proton-Responsive Iridium(III) Complexes journal April 2013
Catalytic Hydrogenation of Carbon Dioxide Using Ir(III)−Pincer Complexes journal October 2009
Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions
  • Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396 https://doi.org/10.1021/jp810292n
journal May 2009
Simultaneous Tuning of Activity and Water Solubility of Complex Catalysts by Acid−Base Equilibrium of Ligands for Conversion of Carbon Dioxide journal January 2007
Catalytic Hydrogenation of Cytotoxic Aldehydes Using Nicotinamide Adenine Dinucleotide (NADH) in Cell Growth Media journal March 2016
Efficient Dehydrogenation of Formic Acid Using an Iron Catalyst journal September 2011
Catalytic interconversion between hydrogen and formic acid at ambient temperature and pressure journal January 2012
Selective Catalytic Synthesis Using the Combination of Carbon Dioxide and Hydrogen: Catalytic Chess at the Interface of Energy and Chemistry journal May 2016
Controlled Generation of Hydrogen from Formic Acid Amine Adducts at Room Temperature and Application in H 2 /O 2 Fuel Cells journal May 2008
The Use of Ureates as Activators for Samarium Diiodide journal July 2016
Secondary Coordination Sphere Interactions Facilitate the Insertion Step in an Iridium(III) CO 2 Reduction Catalyst journal June 2011
CO 2 Hydrogenation to Formate and Methanol as an Alternative to Photo- and Electrochemical CO 2 Reduction journal August 2015
Interaction of N-(aryl)picolinamides with iridium. N–H and C–H bond activations journal October 2008
Catalysis of the electrochemical reduction of carbon dioxide journal January 2013
Highly Efficient Reversible Hydrogenation of Carbon Dioxide to Formates Using a Ruthenium PNP-Pincer Catalyst journal April 2014
Efficient and Mild Carbon Dioxide Hydrogenation to Formate Catalyzed by Fe(II) Hydrido Carbonyl Complexes Bearing 2,6-(Diaminopyridyl)diphosphine Pincer Ligands journal April 2016
Second-coordination-sphere and electronic effects enhance iridium(iii)-catalyzed homogeneous hydrogenation of carbon dioxide in water near ambient temperature and pressure journal January 2012
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals journal July 2007
Simple Continuous High-Pressure Hydrogen Production and Separation System from Formic Acid under Mild Temperatures journal December 2015
Reversible hydrogen storage using CO2 and a proton-switchable iridium catalyst in aqueous media under mild temperatures and pressures journal March 2012
Efficient Cp*Ir Catalysts with Imidazoline Ligands for CO 2 Hydrogenation : Cp*Ir Catalysts with Imidazoline Ligands for CO journal November 2015
Highly efficient hydrogen evolution by decomposition of formic acid using an iridium catalyst with 4,4′-dihydroxy-2,2′-bipyridine journal January 2009
NMR Investigations of Restricted Rotations and Metallotropic Shifts in Rhenium(I) Tricarbonyl Halide Complexes of Pyridyl Carboxamide and Thioamide Ligands journal February 2000
Low-Pressure Hydrogenation of Carbon Dioxide Catalyzed by an Iron Pincer Complex Exhibiting Noble Metal Activity journal September 2011
Extremely Active, Tunable, and pH-Responsive Iridium Water Oxidation Catalysts journal December 2016
Interconversion of Formic Acid and Carbon Dioxide by Proton-Responsive, Half-Sandwich Cp*Ir III Complexes: A Computational Mechanistic Investigation journal December 2015
Highly efficient conversion of carbon dioxide catalyzed by half-sandwich complexes with pyridinol ligand: The electronic effect of oxyanion journal September 2006
Molecular Approaches to the Photocatalytic Reduction of Carbon Dioxide for Solar Fuels journal December 2009

Figures / Tables (5)

Scheme 1(p. 1)figure Scheme 1
Figure 1(p. 2)figure Figure 1
Scheme 2(p. 2)figure Scheme 2
Table 1(p. 3)table Table 1
Scheme 3(p. 4)figure Scheme 3

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CO2 hydrogenation
deprotonated picolinamide ligand
DFT calculations
formate production
hydrogen storage
water-soluble Ir catalysts