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Title: Electrocatalytic Oxidation of 5-Hydroxymethylfurfural to 2,5-furandicarboxylic Acid on Supported Au and Pd Bimetallic Nanoparticles

Abstract

This research explores the potential-dependent electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) in alkaline media over supported Au and Pd nanoparticles and demonstrates the synergistic effects of bimetallic Pd–Au catalysts for the selective formation of 2,5-furandicarboxylic acid (FDCA). Results from electrolysis product analysis at various electrode potentials, along with cyclic voltammetry of HMF and its oxidation intermediates, revealed the unique catalytic properties of Pd and Au for competitive oxidation of alcohol and aldehyde side-groups present in HMF. Aldehyde oxidation was greatly favored over alcohol oxidation on the Au/C catalyst, which was very active for HMF oxidation to 5-hydroxymethyl-2-furancarboxylic acid (HFCA), however high electrode potentials were required for further oxidation of the alcohol group to FDCA. HMF oxidation on Pd/C followed two competitive routes to FDCA and the pathway was dependent on the electrode potential. Oxidation of aldehyde groups occurred much slower on Pd/C than on Au/C at low potentials, but was greatly enhanced at increased potentials or by alloying with Au. It was found that Pd–Au bimetallic catalysts achieved deeply oxidized products (FFCA and FDCA) at lower potentials than monometallic catalysts and the product distribution was dependent on the electrode potential and surface alloy composition. Bimetallic catalysts with 2:1 and 1:2 Pd–Aumore » molar ratios (Pd 2Au 1/C and Pd 1Au 2/C) exhibited advantages of both single components with facile alcohol and aldehyde group oxidation, resulting in greatly improved HMF conversion rate and selectivity to fully oxidized FDCA.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [2];  [1]
  1. Michigan Technological Univ., Houghton, MI (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1265287
DOE Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article
Journal Name:
Green Chemistry
Additional Journal Information:
Journal Volume: 16; Journal Issue: 8; Journal ID: ISSN 1463-9262
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Chadderdon, David, Xin, Le, Qi, Ji, Qiu, Yang, Krishna, Phani, More, Karren Leslie, and Li, Wenzhen. Electrocatalytic Oxidation of 5-Hydroxymethylfurfural to 2,5-furandicarboxylic Acid on Supported Au and Pd Bimetallic Nanoparticles. United States: N. p., 2014. Web. doi:10.1039/C4GC00401A.
Chadderdon, David, Xin, Le, Qi, Ji, Qiu, Yang, Krishna, Phani, More, Karren Leslie, & Li, Wenzhen. Electrocatalytic Oxidation of 5-Hydroxymethylfurfural to 2,5-furandicarboxylic Acid on Supported Au and Pd Bimetallic Nanoparticles. United States. doi:10.1039/C4GC00401A.
Chadderdon, David, Xin, Le, Qi, Ji, Qiu, Yang, Krishna, Phani, More, Karren Leslie, and Li, Wenzhen. Thu . "Electrocatalytic Oxidation of 5-Hydroxymethylfurfural to 2,5-furandicarboxylic Acid on Supported Au and Pd Bimetallic Nanoparticles". United States. doi:10.1039/C4GC00401A.
@article{osti_1265287,
title = {Electrocatalytic Oxidation of 5-Hydroxymethylfurfural to 2,5-furandicarboxylic Acid on Supported Au and Pd Bimetallic Nanoparticles},
author = {Chadderdon, David and Xin, Le and Qi, Ji and Qiu, Yang and Krishna, Phani and More, Karren Leslie and Li, Wenzhen},
abstractNote = {This research explores the potential-dependent electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) in alkaline media over supported Au and Pd nanoparticles and demonstrates the synergistic effects of bimetallic Pd–Au catalysts for the selective formation of 2,5-furandicarboxylic acid (FDCA). Results from electrolysis product analysis at various electrode potentials, along with cyclic voltammetry of HMF and its oxidation intermediates, revealed the unique catalytic properties of Pd and Au for competitive oxidation of alcohol and aldehyde side-groups present in HMF. Aldehyde oxidation was greatly favored over alcohol oxidation on the Au/C catalyst, which was very active for HMF oxidation to 5-hydroxymethyl-2-furancarboxylic acid (HFCA), however high electrode potentials were required for further oxidation of the alcohol group to FDCA. HMF oxidation on Pd/C followed two competitive routes to FDCA and the pathway was dependent on the electrode potential. Oxidation of aldehyde groups occurred much slower on Pd/C than on Au/C at low potentials, but was greatly enhanced at increased potentials or by alloying with Au. It was found that Pd–Au bimetallic catalysts achieved deeply oxidized products (FFCA and FDCA) at lower potentials than monometallic catalysts and the product distribution was dependent on the electrode potential and surface alloy composition. Bimetallic catalysts with 2:1 and 1:2 Pd–Au molar ratios (Pd2Au1/C and Pd1Au2/C) exhibited advantages of both single components with facile alcohol and aldehyde group oxidation, resulting in greatly improved HMF conversion rate and selectivity to fully oxidized FDCA.},
doi = {10.1039/C4GC00401A},
journal = {Green Chemistry},
issn = {1463-9262},
number = 8,
volume = 16,
place = {United States},
year = {2014},
month = {4}
}

Works referenced in this record:

Pd and Pt catalysts modified by alloying with Au in the selective oxidation of alcohols
journal, November 2006


Liquid-Phase Catalytic Processing of Biomass-Derived Oxygenated Hydrocarbons to Fuels and Chemicals
journal, September 2007

  • Chheda, Juben N.; Huber, George W.; Dumesic, James A.
  • Angewandte Chemie International Edition, Vol. 46, Issue 38, p. 7164-7183
  • DOI: 10.1002/anie.200604274

Chemical Routes for the Transformation of Biomass into Chemicals
journal, June 2007

  • Corma, Avelino; Iborra, Sara; Velty, Alexandra
  • Chemical Reviews, Vol. 107, Issue 6, p. 2411-2502
  • DOI: 10.1021/cr050989d

Oxidation of 5-hydroxymethylfurfural over supported Pt, Pd and Au catalysts
journal, February 2011


Gold-Catalyzed Aerobic Oxidation of 5-Hydroxymethylfurfural in Water at Ambient Temperature
journal, July 2009

  • Gorbanev, Yury Y.; Klitgaard, Søren K.; Woodley, John M.
  • ChemSusChem, Vol. 2, Issue 7
  • DOI: 10.1002/cssc.200900059

Biomass into Chemicals: Aerobic Oxidation of 5-Hydroxymethyl-2-furfural into 2,5-Furandicarboxylic Acid with Gold Nanoparticle Catalysts
journal, December 2009


Solvent-Free Oxidation of Primary Carbon-Hydrogen Bonds in Toluene Using Au-Pd Alloy Nanoparticles
journal, January 2011


Electrocatalytic oxidation of glycerol on Pt/C in anion-exchange membrane fuel cell: Cogeneration of electricity and valuable chemicals
journal, May 2012


Chemicals from Renewables: Aerobic Oxidation of Furfural and Hydroxymethylfurfural over Gold Catalysts
journal, February 2008

  • Taarning, Esben; Nielsen, Inger S.; Egeblad, Kresten
  • ChemSusChem, Vol. 1, Issue 1-2
  • DOI: 10.1002/cssc.200700033

Electro-oxidation of glycerol at Pd based nano-catalysts for an application in alkaline fuel cells for chemicals and energy cogeneration
journal, January 2010

  • Simões, Mário; Baranton, Stève; Coutanceau, Christophe
  • Applied Catalysis B: Environmental, Vol. 93, Issue 3-4
  • DOI: 10.1016/j.apcatb.2009.10.008

Oxidation of biomass derived 5-hydroxymethylfurfural using heterogeneous and electrochemical catalysis
journal, November 2012


Surface chemistry of catalysis by gold
journal, March 2004

  • Meyer, R.; Lemire, C.; Shaikhutdinov, Sh. K.
  • Gold Bulletin, Vol. 37, Issue 1-2
  • DOI: 10.1007/BF03215519

Biomass into chemicals: Conversion of sugars to furan derivatives by catalytic processes
journal, September 2010


Production of 5-hydroxymethylfurfural and furfural by dehydration of biomass-derived mono- and poly-saccharides
journal, January 2007

  • Chheda, Juben N.; Román-Leshkov, Yuriy; Dumesic, James A.
  • Green Chem., Vol. 9, Issue 4, p. 342-350
  • DOI: 10.1039/B611568C

Selective electro-conversion of glycerol to glycolate on carbon nanotube supported gold catalyst
journal, January 2012

  • Zhang, Zhiyong; Xin, Le; Qi, Ji
  • Green Chemistry, Vol. 14, Issue 8
  • DOI: 10.1039/c2gc35505a

Supported gold nanoparticles as anode catalyst for anion-exchange membrane-direct glycerol fuel cell (AEM-DGFC)
journal, June 2012


The furan counterpart of poly(ethylene terephthalate): An alternative material based on renewable resources
journal, January 2009

  • Gandini, Alessandro; Silvestre, Armando J. D.; Neto, Carlos Pascoal
  • Journal of Polymer Science Part A: Polymer Chemistry, Vol. 47, Issue 1
  • DOI: 10.1002/pola.23130

Selective oxidation of glycerol with oxygen using mono and bimetallic catalysts based on Au, Pd and Pt metals
journal, May 2005


Selective Oxidation of Glycerol by Highly Active Bimetallic Catalysts at Ambient Temperature under Base-Free Conditions
journal, August 2011


PdAu/C catalysts prepared by plasma sputtering for the electro-oxidation of glycerol
journal, September 2011


Phase Modifiers Promote Efficient Production of Hydroxymethylfurfural from Fructose
journal, June 2006

  • Roman-Leshkov, Yuriy; Chheda, Juben N.; Dumesic, James A.
  • Science, Vol. 312, Issue 5782, p. 1933-1937
  • DOI: 10.1126/science.1126337

5-Hydroxymethylfurfural (HMF) as a building block platform: Biological properties, synthesis and synthetic applications
journal, January 2011

  • Rosatella, Andreia A.; Simeonov, Svilen P.; Frade, Raquel F. M.
  • Green Chemistry, Vol. 13, Issue 4
  • DOI: 10.1039/c0gc00401d

Solvent-Free Oxidation of Primary Alcohols to Aldehydes Using Au-Pd/TiO 2 Catalysts
journal, January 2006


Understanding and Controlling Reactivity of Unsaturated Oxygenates and Polyols on Metal Catalysts
journal, August 2011


Au, Pd (mono and bimetallic) catalysts supported on graphite using the immobilisation method
journal, September 2005


Bimetallic Gold/Palladium Catalysts: Correlation between Nanostructure and Synergistic Effects
journal, May 2008

  • Wang, Di; Villa, Alberto; Porta, Francesca
  • The Journal of Physical Chemistry C, Vol. 112, Issue 23
  • DOI: 10.1021/jp800805e

The Role of Atomic Ensembles in the Reactivity of Bimetallic Electrocatalysts
journal, September 2001


Selective oxidation of 5-hydroxymethyl-2-furfural using supported gold–copper nanoparticles
journal, January 2011

  • Pasini, Thomas; Piccinini, Marco; Blosi, Magda
  • Green Chemistry, Vol. 13, Issue 8
  • DOI: 10.1039/c1gc15355b

Integrated electrocatalytic processing of levulinic acid and formic acid to produce biofuel intermediate valeric acid
journal, January 2014

  • Qiu, Yang; Xin, Le; Chadderdon, David J.
  • Green Chem., Vol. 16, Issue 3
  • DOI: 10.1039/C3GC42254B