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Title: Additive-Free Ruthenium-Catalyzed Hydrogen Production from Aqueous Formaldehyde with High Efficiency and Selectivity

Journal Article · · ACS Catalysis
ORCiD logo [1]; ORCiD logo [2];  [1];  [1];  [3];  [2]; ORCiD logo [2]; ORCiD logo [1]
  1. National Institute of Advanced Industrial Science and Technology (Japan). Research Institute of Energy Frontier, Department of Energy and Environment
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division
  3. Baruch College, CUNY, New York, NY (United States). Department of Natural Sciences
+ Show Author Affiliations

In this study, an efficient water-soluble ruthenium complex was developed for selective hydrogen production from aqueous formaldehyde under mild conditions with a high yield (~95%). Hydrogen production by this catalytic system proceeds without using any additives or organic solvents, leading to a high turnover frequency (8300 h–1) and a record turnover number of 24 000. Additionally, based on mechanistic experiments and density functional theory (DFT) calculations, a step-by-step mechanism has been proposed for the catalytic cycle.

Research Organization:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
Grant/Contract Number:
SC0012704
OSTI ID:
1473638
Report Number(s):
BNL-209075-2018-JAAM
Journal Information:
ACS Catalysis, Vol. 8, Issue 9; ISSN 2155-5435
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 25 works
Citation information provided by
Web of Science

References (37)

A Hydrogen Economy journal June 1972
Hydrogen nexus in a sustainable energy future journal January 2008
Low-temperature aqueous-phase methanol dehydrogenation to hydrogen and carbon dioxide journal February 2013
A homogeneous transition metal complex for clean hydrogen production from methanol–water mixtures journal March 2013
Reusable Homogeneous Catalytic System for Hydrogen Production from Methanol and Water journal July 2014
Base-Free Methanol Dehydrogenation Using a Pincer-Supported Iron Compound and Lewis Acid Co-catalyst journal March 2015
Selective Catalytic Synthesis Using the Combination of Carbon Dioxide and Hydrogen: Catalytic Chess at the Interface of Energy and Chemistry journal May 2016
Efficient Reversible Hydrogen Carrier System Based on Amine Reforming of Methanol journal February 2017
Iron(II) Complexes of the Linear rac- Tetraphos-1 Ligand as Efficient Homogeneous Catalysts for Sodium Bicarbonate Hydrogenation and Formic Acid Dehydrogenation journal January 2015
Reversible hydrogen storage using CO2 and a proton-switchable iridium catalyst in aqueous media under mild temperatures and pressures journal March 2012
CO 2 Hydrogenation to Formate and Methanol as an Alternative to Photo- and Electrochemical CO 2 Reduction journal August 2015
Inside Cover: Efficient Hydrogen Storage and Production Using a Catalyst with an Imidazoline-Based, Proton-Responsive Ligand (ChemSusChem 6/2017) journal March 2017
Metal-Nanoparticle-Catalyzed Hydrogen Generation from Formic Acid journal May 2017
A Charge/Discharge Device for Chemical Hydrogen Storage and Generation journal September 2011
Catalytic CO 2 Hydrogenation to Formate by a Ruthenium Pincer Complex journal September 2013
Base-free hydrogenation of CO 2 to formic acid in water with an iridium complex bearing a N,N′-diimine ligand journal January 2016
Changing the Mechanism for CO 2 Hydrogenation Using Solvent-Dependent Thermodynamics journal October 2017
Reversible Hydrogenation of Carbon Dioxide to Formic Acid and Methanol: Lewis Acid Enhancement of Base Metal Catalysts journal February 2017
Dehydrogenation of Formic Acid Catalyzed by a Ruthenium Complex with an N,N ′-Diimine Ligand journal December 2016
Hydrogen energy future with formic acid: a renewable chemical hydrogen storage system journal January 2016
Formic acid as a hydrogen storage material – development of homogeneous catalysts for selective hydrogen release journal January 2016
Formic Acid as a Hydrogen Energy Carrier journal December 2016
Homogeneous Catalysis for Sustainable Hydrogen Storage in Formic Acid and Alcohols journal October 2017
Selective and mild hydrogen production using water and formaldehyde journal April 2014
Homogeneously catalysed conversion of aqueous formaldehyde to H2 and carbonate journal April 2017
Water decontamination with hydrogen production using microwave-formed minute-made ruthenium catalysts journal January 2016
Catalytic hydrogen production from paraformaldehyde and water using an organoiridium complex journal January 2015
Hydrogen Production from a Methanol-Water Solution Catalyzed by an Anionic Iridium Complex Bearing a Functional Bipyridonate Ligand under Weakly Basic Conditions journal June 2015
Oxygen-Controlled Hydrogen Evolution Reaction: Molecular Oxygen Promotes Hydrogen Production from Formaldehyde Solution Using Ag/MgO Nanocatalyst journal January 2017
Highly Efficient and Selective Methanol Production from Paraformaldehyde and Water at Room Temperature journal May 2018
Chemical and Electrochemical Generation of Hydride-Forming Catalytic Intermediates (bpy)M(CnRn): M = Rh, Ir (n = 5); M = Ru, Os (n = 6). Coordinatively Unsaturated Ground State Models of MLCT Excited States? journal September 1994
Kinetics and Mechanism of the Stereochemical Isomerization of an Arene−Ruthenium Complex of the Atropisomeric Ligand 1,1‘-Biphenyl-2,2‘-diamine journal November 1999
Origin of Acid–Base Catalytic Effects on Formaldehyde Hydration journal November 2016
NMR Studies of the Equilibria and Reaction Rates in Aqueous Solutions of Formaldehyde journal March 2015
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
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
Theoretical Mechanistic Study of Rhodium(I) Phosphine-Catalyzed H/D Exchange Processes in Aqueous Solutions journal June 2005

Cited By (2)

Base-free hydrogen generation from formaldehyde and water catalyzed by copper nanoparticles embedded on carbon sheets journal January 2019
Chemoenzymatic Hydrogen Production from Methanol through the Interplay of Metal Complexes and Biocatalysts journal February 2019

Linked Research (1)

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37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
dehydrogenation
formaldehyde
H2 production
homogeneous catalysis
ruthenium complex