[Last updated: Apr 13,
2011]
Yuichiro HIMEDA
National
Institute of Advanced Industrial Science and Technology,
Tsukuba
Central 5-2, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan
E-mail:
himeda.y(atmark)aist.go.jp
[Research]
The catalyst shows the highest
efficiency in hydrogenation of carbon dioxide (fixation of carbon dioxide
and storage of hydrogen) under basic conditions, and
decomposition of formic acid (production of hydrogen) under acid conditions.
Hydrogenation of bicarbonate with high catalytic activity and reusability of
the catalyst without waste generation by automatic tuning of the catalytic
activity and water solubility of the catalyst through the acid-base equilibrium
of the catalyst ligand is demonstrated. The oxyanion generated from the phenol
hydroxy group in bipyridine ligand played significant roles in the electronic
effect and polarity. The strong electron-donating ability of oxyanion resulted
in a remarkably high catalytic activity, which was over 1000 times greater than
that of an unsubstituted bipyridine complex. The catalyst design concept and
the excellent properties of the ligands are expected to have significantly
broader implications for the design of new homogeneous catalysts.
On the other hand, the
efficient evolution of CO-free hydrogen by the decomposition of formic acid in
water was achieved. The highest catalytic activity and an almost complete
consumption of formic acid were obtained for the catalytic system. Furthermore,
it was found that hydrogen could be generated even at elevated pressures.
Keywords
Homogeneous Catalysis;
Organometallic catalyst
CO2 fixation; H2 storage; energy conversion
Catalyst
tuning; Catalyst design; pH dependence
Green
chemistry; Aqueous reaction; Catalyst recycling
Hydrogenation;
Transfer hydrogenation
H/D
exchange; Deuterogenation
[Previous studies]
Synthesis of
Polysubstituted Cyclopentadienes Using Allylidenephosphoranes and its
Applications
[Publication list]
Himeda, Y.; Miyazawa, S.; Hirose, T.
Interconversion between Formic Acid and H2/CO2
using Rhodium and Ruthenium Catalysts for CO2 Fixation
and H2
Storage.
ChemSusChem 2011, 4 (4),
487–493. <doi>
Himeda, Y.
“Utilization of Carbon
Dioxide as a Hydrogen Storage Material: Hydrogenation of Carbon Dioxide and
Decomposition of Formic Acid Using Iridium Complex Catalysts” in Advances in
CO2 Conversion and Utilization
ACS Symposium Series, 2010, 1056, Chapter
9, pp 141–153. <doi>
Himeda, Y.
Highly efficient hydrogen
evolution by decomposition of formic acid using iridium catalyst with
4,4'-dihydroxy-2,2'-bipyridine.
Green Chemistry, 2009, 11,
2018–2022. <doi>
Himeda, Y.; Miyazawa, S.; Onozawa-Komatsuzaki,
N.; Hirose, T.; Kasuga, K.
Catalytic (transfer)
deuterogenation in D2O as deuterium source with H2 and HCO2H as electron
sources.
Dalton Trans., 2009, (32), 6286–6288. <doi>
Himeda, Y.;
Onozawa-Komatsuzaki, N.; Miyazawa, S.; Sugihara, H.; Hirose, T.; Kasuga, K.
pH-Dependent Catalytic
Activity and Chemoselectivity in Transfer Hydrogenation Catalyzed by Iridium
Complex with 4,4’-Dihydroxy-2,2’-bipyridine.
Chemistry-A European
Journal 2008, (35), 11076-11081.<doi>
Himeda, Y.
Conversion
of CO2 into Formate by Homogeneously
Catalyzed Hydrogenation in Water: Tuning Catalytic Activity and Water
Solubility through the Acid–Base Equilibrium of the Ligand.
European Journal
Inorganic Chemistry 2007, (25), 3927–3941.<doi>
Himeda, Y.;
Onozawa-Komatsuzaki, N.; Sugihara, H.; Kasuga, K.
Simultaneous tuning of
activity and water solubility of complex catalysts by acid-base equilibrium of
ligands for conversion of carbon dioxide.
Organometallics 2007, 26, (3), 702–712. <doi>
Himeda, Y.;
Onozawa-Komatsuzaki, N.; Sugihara, H.; Kasuga, K.
Highly efficient
conversion of carbon dioxide catalyzed by half-sandwich complexes with
pyridinol ligand: The electronic effect of oxyanion.
Journal of
Photochemistry and Photobiology A-Chemistry 2006, 182, (3), 306–309. <doi>
Himeda, Y.;
Onozawa-Komatsuzaki, N.; Sugihara, H.; Kasuga, K.
Recyclable catalyst for
conversion of carbon dioxide into formate attributable to an oxyanion on the
catalyst ligand.
Journal of the American
Chemical Society 2005, 127, (38), 13118–13119. <doi>
Himeda, Y.;
Onozawa-Komatsuzaki, N.; Sugihara, H.; Arakawa, H.; Kasuga, K.
Half-sandwich complexes
with dihydroxy polypyridine: Water-soluble, highly efficient catalysts for
hydrogenation of bicarbonate attributable to electron-donating ability of
oxyanion on catalyst ligand.
Studies in Surface
Science and Catalysis 2004, 153, 263-266.
Himeda, Y.;
Onozawa-Komatsuzaki, N.; Sugihara, H.; Arakawa, H.; Kasuga, K.
Half-sandwich complexes
with 4,7-dihydroxy-1,10-phenanthroline: Water-soluble, highly efficient
catalysts for hydrogenation of bicarbonate attributable to the generation of an
oxyanion on the catalyst ligand.
Organometallics 2004, 23, (7), 1480-1483. <doi>
Himeda, Y.;
Onozawa-Komatsuzaki, N.; Sugihara, H.; Arakawa, H.; Kasuga, K.
Transfer hydrogenation of
a variety of ketones catalyzed by rhodium complexes in aqueous solution and
their application to asymmetric reduction using chiral Schiff base ligands.
Journal of Molecular
Catalysis A-Chemical 2003, 195, (1-2), 95-100. <doi>
Hirose, T.; Maeno, Y.;
Himeda, Y.
Photocatalytic carbon
dioxide photoreduction by Co(bpy)32+ sensitized by Ru(bpy)32+ fixed to cation exchange polymer.
Journal of Molecular
Catalysis A-Chemical 2003, 193, (1-2), 27-32. <doi>
Komatsuzaki, N.; Himeda, Y.;
Hirose, T.; Sugihara, H.; Kasuga, K.
Synthesis and photochemical
properties of ruthenium-cobalt and ruthenium-nickel dinuclear complexes.
Bulletin of the Chemical
Society of Japan 1999, 72, (4), 725-731. <doi>
Himeda, Y.; Tanaka, Y.; Ueda,
I.; Hatanaka, M.
Convenient synthesis of
substituted cyclopentenones via [3+2] annulation of
allylidenetriphenylphosphorane with 1,2-diacylethylenes: application to
synthesis of (+/-)-methyl dehydrojasmonate.
Journal of the Chemical
Society-Perkin Transactions 1 1998, (8), 1389-1396. <doi>
Himeda, Y.; Yamataka, H.; Ueda,
I.; Hatanaka, M.
[3+2] Annulation of
allylidenetriphenylphosphorane with 1,2-diacylethylenes and
1,2-diacylacetylenes: A one-step synthesis of tri- and tetrasubstituted
cyclopentadienes and fulvenes.
Journal of Organic
Chemistry 1997, 62, (19), 6529-6538. <doi>
Himeda, Y.; Ueda, I.;
Hatanaka, M.
A new one-step synthesis of
functionalized fulvenes.
Chemistry Letters 1996, (1), 71-72. <doi>
Himeda, Y.; Hatanaka, M.;
Ueda, I.
[3+2]-Annulation of
Allylidene(Triphenyl)Phosphorane with 1,2-Diacylethylenes - Synthesis of
Substituted Cyclopentadienes.
Journal of the Chemical
Society-Chemical Communications 1995, (4), 449-450. <doi>
Hatanaka, M.; Himeda, Y.;
Tanaka, Y.; Ueda, I.
Cyclopentenones from
2-Ethoxyallylidene(Triphenyl)Phosphorane and 1,2-Diacylethylenes - Synthesis of
(+/-)-Methyl Dehydrojasmonate.
Tetrahedron Letters 1995, 36, (18), 3211-3214. <doi>
Hatanaka, M.; Himeda, Y.;
Imashiro, R.; Tanaka, Y.; Ueda, I.
Allylidenetriphenylphosphorane
as a Bifunctional Reagent - Synthesis of Cyclopentenones and
Alpha,Beta-Unsaturated Ketones with
(3-(Alkoxycarbonyl)-2-Ethoxy-2-Propenylidene)Triphenylphosphorane.
Journal of Organic
Chemistry 1994, 59, (1), 111-119.
Himeda, Y.; Hiratani, K.;
Kasuga, K.; Hirose, T.
A New
Bis(Benzo-15-Crown-5)-Type Ionophore Having 1,10-Phenanthroline Moiety as a
Highly-Selective Potassium Ion-Carrier.
Chemistry Letters 1993, (9), 1475-1478. <doi>
Hatanaka, M.; Tanaka, Y.;
Himeda, Y.; Ueda, I.
A Single-Step Synthesis of
4-Hydroxycyclopentenones from
3-Ethoxycarbonyl-2-Oxo-Propylidenetriphenylphosphorane and Glyoxals.
Tetrahedron Letters 1993, 34, (30), 4837-4840. <doi>
Hatanaka, M.; Himeda, Y.;
Ueda, I.
[3+2]-Annulation Using
Allylidene(Triphenyl)Phosphoranes - a One-Step Synthesis of Cyclopentadienes.
Journal of the Chemical
Society-Perkin Transactions 1 1993, (19), 2269-2274. <doi>
Himeda, Y.; Hiratani, K.;
Hatanaka, M.; Ueda, I.
Intramolecular Diels-Alder
Reaction of 1-Ethoxycarbonyl-4-Alkenylcyclopentadienes.
Journal of the Chemical
Society-Chemical Communications 1992, (22), 1684-1685. <doi>
Hatanaka, M.; Himeda, Y.;
Ueda, I.
Cyclopentenones from
Allylidene Triphenylphosphoranes and Alpha-Halocarbonyl Compounds.
Tetrahedron Letters 1991, 32, (35), 4521-4524. <doi>
Hatanaka, M.; Himeda, Y.;
Ueda, I.
The Reaction of Allylidene
Triphenylphosphoranes with Alpha-Halocarbonyl Compounds - a Convenient Synthesis
of Cyclopentadienes.
Journal of the Chemical
Society-Chemical Communications 1990, (7), 526-527. <doi>