Base-free selective oxidation of pectin derived galacturonic acid to galactaric acid using supported gold catalysts

Rajeesh Kumar Pazhavelikkakath Purushothaman, F. van der Klis, A.E. Frissen, J. van Haveren, A. Mayoral, A. van der Bent, D.S. van Es*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

4 Citations (Scopus)

Abstract

Agricultural residues like sugar beet pulp (SBP) are an interesting feedstock for the production of 2nd generation bio-based chemicals and materials. The pectin fraction of SBP is rich in galacturonic acid (GalA), a C6 sugar acid. The oxidation of this uronic acid at C1 yields galactaric acid (GA), which has several industrially interesting properties. It was previously shown that the Au catalysed oxidation of uronic acids under basic conditions is highly effective, yet leads to the co-production of salts. Hence, here we report for the first time on the oxidation of an acidic carbohydrate substrate, GalA, at its autogenic pH (2.2) in water, using carbon supported gold nanoparticles, under mild conditions in the presence of molecular oxygen. The comparison of the Au/C catalyst prepared by a colloidal deposition method with benchmark commercially available metal oxide supported gold catalysts shows that under acidic conditions, the Au/C catalyst is more active and more selective than Au/TiO2, and more stable than Au/Al2O3. The difference in selectivity is attributed to the H2O2 mediated chain scission reaction of the substrate (GalA) which is observed only in the case of metal oxide supported Au catalysts. The Au/C catalyst shows 100% GA selectivity at 76% GalA conversion (333 K, 21 h batch time) and a GA yield of up to 95% was obtained at 353 K. Detailed characterization of the fresh and spent Au/C catalysts by ICP-OES, TEM and XPS analyses showed no gold leaching, particle sintering or change in metal composition. The Au/C catalyst was fully regenerated by a mild alkaline wash, and used in five consecutive runs without any significant decrease in activity or selectivity. Labelling experiments with 18O2 and H2 18O2 revealed that under base-free conditions, the oxygen incorporated in the aldaric acid originates from the solvent water.

Original languageEnglish
Pages (from-to)2763-2774
JournalGreen Chemistry
Volume20
Issue number12
DOIs
Publication statusPublished - 1 Jan 2018

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Gold
gold
catalyst
oxidation
Oxidation
Catalysts
Acids
acid
Sugar beets
Uronic Acids
Metals
Oxides
Pulp
Sugar Acids
sugar beet
Agricultural wastes
Water
Molecular oxygen
Catalyst selectivity
Substrates

Cite this

@article{479b6b4493534b7fb3ae5f43c4513e38,
title = "Base-free selective oxidation of pectin derived galacturonic acid to galactaric acid using supported gold catalysts",
abstract = "Agricultural residues like sugar beet pulp (SBP) are an interesting feedstock for the production of 2nd generation bio-based chemicals and materials. The pectin fraction of SBP is rich in galacturonic acid (GalA), a C6 sugar acid. The oxidation of this uronic acid at C1 yields galactaric acid (GA), which has several industrially interesting properties. It was previously shown that the Au catalysed oxidation of uronic acids under basic conditions is highly effective, yet leads to the co-production of salts. Hence, here we report for the first time on the oxidation of an acidic carbohydrate substrate, GalA, at its autogenic pH (2.2) in water, using carbon supported gold nanoparticles, under mild conditions in the presence of molecular oxygen. The comparison of the Au/C catalyst prepared by a colloidal deposition method with benchmark commercially available metal oxide supported gold catalysts shows that under acidic conditions, the Au/C catalyst is more active and more selective than Au/TiO2, and more stable than Au/Al2O3. The difference in selectivity is attributed to the H2O2 mediated chain scission reaction of the substrate (GalA) which is observed only in the case of metal oxide supported Au catalysts. The Au/C catalyst shows 100{\%} GA selectivity at 76{\%} GalA conversion (333 K, 21 h batch time) and a GA yield of up to 95{\%} was obtained at 353 K. Detailed characterization of the fresh and spent Au/C catalysts by ICP-OES, TEM and XPS analyses showed no gold leaching, particle sintering or change in metal composition. The Au/C catalyst was fully regenerated by a mild alkaline wash, and used in five consecutive runs without any significant decrease in activity or selectivity. Labelling experiments with 18O2 and H2 18O2 revealed that under base-free conditions, the oxygen incorporated in the aldaric acid originates from the solvent water.",
author = "{Pazhavelikkakath Purushothaman}, {Rajeesh Kumar} and {van der Klis}, F. and A.E. Frissen and {van Haveren}, J. and A. Mayoral and {van der Bent}, A. and {van Es}, D.S.",
year = "2018",
month = "1",
day = "1",
doi = "10.1039/c8gc00103k",
language = "English",
volume = "20",
pages = "2763--2774",
journal = "Green Chemistry",
issn = "1463-9262",
publisher = "Royal Society of Chemistry",
number = "12",

}

Base-free selective oxidation of pectin derived galacturonic acid to galactaric acid using supported gold catalysts. / Pazhavelikkakath Purushothaman, Rajeesh Kumar; van der Klis, F.; Frissen, A.E.; van Haveren, J. ; Mayoral, A.; van der Bent, A.; van Es, D.S.

In: Green Chemistry, Vol. 20, No. 12, 01.01.2018, p. 2763-2774.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Base-free selective oxidation of pectin derived galacturonic acid to galactaric acid using supported gold catalysts

AU - Pazhavelikkakath Purushothaman, Rajeesh Kumar

AU - van der Klis, F.

AU - Frissen, A.E.

AU - van Haveren, J.

AU - Mayoral, A.

AU - van der Bent, A.

AU - van Es, D.S.

PY - 2018/1/1

Y1 - 2018/1/1

N2 - Agricultural residues like sugar beet pulp (SBP) are an interesting feedstock for the production of 2nd generation bio-based chemicals and materials. The pectin fraction of SBP is rich in galacturonic acid (GalA), a C6 sugar acid. The oxidation of this uronic acid at C1 yields galactaric acid (GA), which has several industrially interesting properties. It was previously shown that the Au catalysed oxidation of uronic acids under basic conditions is highly effective, yet leads to the co-production of salts. Hence, here we report for the first time on the oxidation of an acidic carbohydrate substrate, GalA, at its autogenic pH (2.2) in water, using carbon supported gold nanoparticles, under mild conditions in the presence of molecular oxygen. The comparison of the Au/C catalyst prepared by a colloidal deposition method with benchmark commercially available metal oxide supported gold catalysts shows that under acidic conditions, the Au/C catalyst is more active and more selective than Au/TiO2, and more stable than Au/Al2O3. The difference in selectivity is attributed to the H2O2 mediated chain scission reaction of the substrate (GalA) which is observed only in the case of metal oxide supported Au catalysts. The Au/C catalyst shows 100% GA selectivity at 76% GalA conversion (333 K, 21 h batch time) and a GA yield of up to 95% was obtained at 353 K. Detailed characterization of the fresh and spent Au/C catalysts by ICP-OES, TEM and XPS analyses showed no gold leaching, particle sintering or change in metal composition. The Au/C catalyst was fully regenerated by a mild alkaline wash, and used in five consecutive runs without any significant decrease in activity or selectivity. Labelling experiments with 18O2 and H2 18O2 revealed that under base-free conditions, the oxygen incorporated in the aldaric acid originates from the solvent water.

AB - Agricultural residues like sugar beet pulp (SBP) are an interesting feedstock for the production of 2nd generation bio-based chemicals and materials. The pectin fraction of SBP is rich in galacturonic acid (GalA), a C6 sugar acid. The oxidation of this uronic acid at C1 yields galactaric acid (GA), which has several industrially interesting properties. It was previously shown that the Au catalysed oxidation of uronic acids under basic conditions is highly effective, yet leads to the co-production of salts. Hence, here we report for the first time on the oxidation of an acidic carbohydrate substrate, GalA, at its autogenic pH (2.2) in water, using carbon supported gold nanoparticles, under mild conditions in the presence of molecular oxygen. The comparison of the Au/C catalyst prepared by a colloidal deposition method with benchmark commercially available metal oxide supported gold catalysts shows that under acidic conditions, the Au/C catalyst is more active and more selective than Au/TiO2, and more stable than Au/Al2O3. The difference in selectivity is attributed to the H2O2 mediated chain scission reaction of the substrate (GalA) which is observed only in the case of metal oxide supported Au catalysts. The Au/C catalyst shows 100% GA selectivity at 76% GalA conversion (333 K, 21 h batch time) and a GA yield of up to 95% was obtained at 353 K. Detailed characterization of the fresh and spent Au/C catalysts by ICP-OES, TEM and XPS analyses showed no gold leaching, particle sintering or change in metal composition. The Au/C catalyst was fully regenerated by a mild alkaline wash, and used in five consecutive runs without any significant decrease in activity or selectivity. Labelling experiments with 18O2 and H2 18O2 revealed that under base-free conditions, the oxygen incorporated in the aldaric acid originates from the solvent water.

U2 - 10.1039/c8gc00103k

DO - 10.1039/c8gc00103k

M3 - Article

VL - 20

SP - 2763

EP - 2774

JO - Green Chemistry

JF - Green Chemistry

SN - 1463-9262

IS - 12

ER -