Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Single-atom gold oxo-clusters prepared in alkaline solutions catalyse the heterogeneous methanol self-coupling reactions

Journal Article · · Nature Chemistry
 [1]; ORCiD logo [1]; ORCiD logo [2];  [1];  [2]; ORCiD logo [1];  [2];  [3];  [1];  [1];  [1];  [1]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [5];  [2]; ORCiD logo [1]
  1. Tufts Univ., Medford, MA (United States)
  2. Univ. of Wisconsin, Madison, WI (United States)
  3. Stony Brook Univ., NY (United States)
  4. Argonne National Lab. (ANL), Argonne, IL (United States)
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
+ Show Author Affiliations

We report the direct use of inorganometallic gold complexes formed in alkaline solutions as robust heterogeneous catalysts. Specifically, mononuclear gold complexes with the gold atom surrounded by a shell of Na cations through -O- linkages were prepared by dissolving Au(OH)3 in highly alkaline solutions of NaOH. The complexes remain intact upon impregnation onto supports or after drying in air to a crystalline powder. Supported catalysts containing exclusively atomic gold at loadings up to 1.2 wt.% Au were prepared. Either in supported or unsupported form, the mononuclear gold-centered oxo-clusters catalyze the selective methanol dehydrogenation reaction to methyl formate (MF) and hydrogen; a reaction of industrial interest as well as the key step in methanol steam reforming. The [Au1-Ox]- center was identified as the active catalytic site by experimental characterization and density functional theory studies. The methanol dehydrogenation reaction mechanism proceeds via the self-coupling of methanol to MF. No oxygen supply is necessary. Hence, hydrogen rather than water is produced at 2:1 (stoichiometric) molar ratio to MF. The dried crystalline powder of the solution was used as an unsupported catalyst, showing the same chemistry as the supported clusters. Ab initio molecular dynamics (AIMD) simulations of methanol self-coupling on the mononuclear gold clusters revealed the formation of formate spectators on the clusters under reaction conditions, also corroborated by in situ DRIFTS. The inclusion of these spectators proved crucial towards the accurate description of the energetics of self-coupling of methanol on these clusters, thus unravelling the nature of the active site. Catalyst stability up to 250-300 oC in reaction conditions is demonstrated.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States); Tufts Univ., Medford, MA (United States); UChicago, LLC., Argonne, IL (United States); Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
AC02-06CH11357; FG02-05ER15730; FG02-05ER15731
OSTI ID:
1602429
Journal Information:
Nature Chemistry, Journal Name: Nature Chemistry Journal Issue: 12 Vol. 11; ISSN 1755-4330
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English

References (41)

Shape and Crystal-Plane Effects of Nanoscale Ceria on the Activity of Au-CeO2 Catalysts for the Water–Gas Shift Reaction journal March 2008
Selectivity Control in Gold-Mediated Esterification of Methanol journal May 2009
Shape and Crystal-Plane Effects of Nanoscale Ceria on the Activity of Au-CeO2 Catalysts for the Water–Gas Shift Reaction journal March 2008
Selectivity Control in Gold-Mediated Esterification of Methanol journal May 2009
Methanol Steam Reforming for Hydrogen Production journal December 2007
Comparison of the activity of Au/CeO2 and Au/Fe2O3 catalysts for the CO oxidation and the water-gas shift reactions journal June 2007
FT-IR study of methanol, formaldehyde and methyl formate adsorption on the surface of Mo/Sn oxide catalyst journal July 2006
Activity and stability of low-content gold–cerium oxide catalysts for the water–gas shift reaction journal March 2005
Ideal Pt loading for a Pt/CeO2-based catalyst stabilized by a Pt–O–Ce bond journal August 2010
From model studies on Au(111) to working conditions with unsupported nanoporous gold catalysts: Oxygen-assisted coupling reactions journal December 2013
An IR study of methanol steam reforming over ex-hydrotalcite Cu–Zn–Al catalysts journal April 2007
Agglomeration, support effects, and CO adsorption on Au/TiO2(110) prepared by ion beam deposition journal March 2005
Methanol Steam Reforming for Hydrogen Production journal October 2007
Methyl Formate Formation from Methanol Oxidation Using Supported Gold–Palladium Nanoparticles journal December 2014
Mechanism of selective methanol oxidation over vanadium oxide-titanium oxide catalysts: a FT-IR and flow reactor study journal September 1987
The Solubility of Gold Hydroxide in Alkali and Equilibria in the Saturated Solutions 1 journal June 1938
Atomically Dispersed Au–(OH) x Species Bound on Titania Catalyze the Low-Temperature Water-Gas Shift Reaction journal March 2013
A Common Single-Site Pt(II)–O(OH) x – Species Stabilized by Sodium on “Active” and “Inert” Supports Catalyzes the Water-Gas Shift Reaction journal March 2015
Hydrogen Production from Methanol over Gold Supported on ZnO and CeO 2 Nanoshapes journal September 2010
Low-temperature hydrogen production from water and methanol using Pt/α-MoC catalysts journal March 2017
Single-atom catalysis of CO oxidation using Pt1/FeOx journal July 2011
Dynamic restructuring drives catalytic activity on nanoporous gold–silver alloy catalysts journal December 2016
The concept, reality and utility of single-site heterogeneous catalysts (SSHCs) journal January 2014
Oxidation of methanol to methyl formate over supported Pd nanoparticles: insights into the reaction mechanism at low temperature journal January 2014
Active gold species on cerium oxide nanoshapes for methanol steam reforming and the water gas shift reactions journal January 2010
The formation of gold sols in alkaline solutions journal January 1938
Stable iridium dinuclear heterogeneous catalysts supported on metal-oxide substrate for solar water oxidation journal March 2018
Evolution of gold structure during thermal treatment of Au/FeOx catalysts revealed by aberration-corrected electron microscopy journal April 2009
Origin and Activity of Oxidized Gold in Water-Gas-Shift Catalysis journal May 2005
Gold(III)-CO and gold(III)-CO 2 complexes and their role in the water-gas shift reaction journal October 2015
Active Nonmetallic Au and Pt Species on Ceria-Based Water-Gas Shift Catalysts journal August 2003
Solvent-Free Oxidation of Primary Alcohols to Aldehydes Using Au-Pd/TiO 2 Catalysts journal January 2006
Nanoporous Gold Catalysts for Selective Gas-Phase Oxidative Coupling of Methanol at Low Temperature journal January 2010
Alkali-Stabilized Pt-OHx Species Catalyze Low-Temperature Water-Gas Shift Reactions journal September 2010
Small Gold Clusters Formed in Solution Give Reaction Turnover Numbers of 107 at Room Temperature journal December 2012
Catalytically active Au-O(OH) x - species stabilized by alkali ions on zeolites and mesoporous oxides journal November 2014
Photochemical route for synthesizing atomically dispersed palladium catalysts journal May 2016
Thermally stable single-atom platinum-on-ceria catalysts via atom trapping journal July 2016
Identification of single-site gold catalysis in acetylene hydrochlorination journal March 2017
Activation of surface lattice oxygen in single-atom Pt/CeO 2 for low-temperature CO oxidation journal December 2017
Atomically Dispersed Supported Metal Catalysts journal July 2012

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY