Influence of Reaction Parameters on Nanogold-Catalyzed Glucose and Xylose Oxidation: A Joint Experimental and DFT Study

Jay Pee Oña; Laura Laverdure; Rose-Marie Latonen; Narendra Kumar; Markus Peurla; Ilari Angervo; Karoliina Honkala; Henrik Grénman

doi:10.1021/acscatal.3c04929

Influence of Reaction Parameters on Nanogold-Catalyzed Glucose and Xylose Oxidation: A Joint Experimental and DFT Study

Jay Pee Oña, Laura Laverdure, Rose-Marie Latonen, Narendra Kumar, Markus Peurla, Ilari Angervo, Karoliina Honkala, Henrik Grénman^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › Scientific › peer-review

5 Citations (Scopus)

Abstract

The electrocatalytic oxidation (ECO) of glucose on gold requires alkaline conditions and relatively high potentials (>0.3VRHE). Although the adsorption of hydroxide ions (OHads) is also known to occur under these conditions, the generally accepted proton-coupled electron transfer mechanism for sugar ECO does not explicitly state the role of OHads in the sugar adsorption or oxidation steps. To investigate this, we carried out a combined experimental and density functional theory (DFT) study on the ECO of glucose and xylose over a nanogold catalyst under temperature and pH control. Grandcanonical DFT (GC-DFT) was used to identify the preferred reaction mechanism in which OHads facilitates the thermodynamically feasible formation of gluconic and xylonic acid. Calculated results also showed that OHads plays a role in improving the acid selectivity. Constant-potential electrolyses in sugar solutions were performed using mesoporous (Sibunit) carbon-supported Au nanoparticles (AuNPs) with an average cluster size of 4.7nm. Experimental results showed that the highest conversions for glucose (57.7%) and xylose (49.4%) were obtained at 25°C and pH12.5, with gluconic and xylonic acid selectivity of 81.5 and 87.8 %, respectively. The catalytic activities were high considering the low Au loading (∼0.1%wt). Higher pH led to a decrease in the ECO rate possibly due to excess hydroxide ions blocking active sites for sugar adsorption. Our results highlight the importance of computational studies in elucidating reaction mechanisms for sugar ECO where sugar acids are the main oxidation products. This is crucial in designing reaction systems for the viable production of these value-added chemicals from biomass.

Original language	English
Pages (from-to)	1532-1544
Number of pages	12
Journal	ACS Catalysis
Volume	14
Issue number	3
DOIs	https://doi.org/10.1021/acscatal.3c04929
Publication status	Published - 2 Feb 2024
MoE publication type	A1 Journal article-refereed

Funding

J.P.O., R.M.K., N.K., M.P., I.A., and H.G. were supported by the Tiina and Antti Herlin Foundation (Finland) under the FosToBioH2 (From fossil to biohydrogen in Finnish (bio)industry─utilizing electrocatalysis in Aqueous Phase Reforming of hemicelluloses) project at Åbo Akademi University, Finland. They would also like to thank the Electron Microscopy Laboratory, Institute of Biomedicine, University of Turku, and Biocenter Finland for the TEM images, and the Wihuri Physical Laboratory, Department of Physics and Astronomy, University of Turku for the XRD analysis. L.L. would like to thank Dr Timo Weckman for helpful discussions about DockOnSurf. Computational resources were provided by the CSC-IT Center for Science, Espoo, Finland. L.L. and K.H. were supported by Academy of Finland grant no. 351583.

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Cite this

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title = "Influence of Reaction Parameters on Nanogold-Catalyzed Glucose and Xylose Oxidation: A Joint Experimental and DFT Study",

abstract = "The electrocatalytic oxidation (ECO) of glucose on gold requires alkaline conditions and relatively high potentials (>0.3VRHE). Although the adsorption of hydroxide ions (OHads) is also known to occur under these conditions, the generally accepted proton-coupled electron transfer mechanism for sugar ECO does not explicitly state the role of OHads in the sugar adsorption or oxidation steps. To investigate this, we carried out a combined experimental and density functional theory (DFT) study on the ECO of glucose and xylose over a nanogold catalyst under temperature and pH control. Grandcanonical DFT (GC-DFT) was used to identify the preferred reaction mechanism in which OHads facilitates the thermodynamically feasible formation of gluconic and xylonic acid. Calculated results also showed that OHads plays a role in improving the acid selectivity. Constant-potential electrolyses in sugar solutions were performed using mesoporous (Sibunit) carbon-supported Au nanoparticles (AuNPs) with an average cluster size of 4.7nm. Experimental results showed that the highest conversions for glucose (57.7\%) and xylose (49.4\%) were obtained at 25°C and pH12.5, with gluconic and xylonic acid selectivity of 81.5 and 87.8 \%, respectively. The catalytic activities were high considering the low Au loading (∼0.1\%wt). Higher pH led to a decrease in the ECO rate possibly due to excess hydroxide ions blocking active sites for sugar adsorption. Our results highlight the importance of computational studies in elucidating reaction mechanisms for sugar ECO where sugar acids are the main oxidation products. This is crucial in designing reaction systems for the viable production of these value-added chemicals from biomass.",

author = "O{\~n}a, \{Jay Pee\} and Laura Laverdure and Rose-Marie Latonen and Narendra Kumar and Markus Peurla and Ilari Angervo and Karoliina Honkala and Henrik Gr{\'e}nman",

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T2 - A Joint Experimental and DFT Study

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AU - Latonen, Rose-Marie

AU - Kumar, Narendra

AU - Peurla, Markus

AU - Angervo, Ilari

AU - Honkala, Karoliina

AU - Grénman, Henrik

PY - 2024/2/2

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N2 - The electrocatalytic oxidation (ECO) of glucose on gold requires alkaline conditions and relatively high potentials (>0.3VRHE). Although the adsorption of hydroxide ions (OHads) is also known to occur under these conditions, the generally accepted proton-coupled electron transfer mechanism for sugar ECO does not explicitly state the role of OHads in the sugar adsorption or oxidation steps. To investigate this, we carried out a combined experimental and density functional theory (DFT) study on the ECO of glucose and xylose over a nanogold catalyst under temperature and pH control. Grandcanonical DFT (GC-DFT) was used to identify the preferred reaction mechanism in which OHads facilitates the thermodynamically feasible formation of gluconic and xylonic acid. Calculated results also showed that OHads plays a role in improving the acid selectivity. Constant-potential electrolyses in sugar solutions were performed using mesoporous (Sibunit) carbon-supported Au nanoparticles (AuNPs) with an average cluster size of 4.7nm. Experimental results showed that the highest conversions for glucose (57.7%) and xylose (49.4%) were obtained at 25°C and pH12.5, with gluconic and xylonic acid selectivity of 81.5 and 87.8 %, respectively. The catalytic activities were high considering the low Au loading (∼0.1%wt). Higher pH led to a decrease in the ECO rate possibly due to excess hydroxide ions blocking active sites for sugar adsorption. Our results highlight the importance of computational studies in elucidating reaction mechanisms for sugar ECO where sugar acids are the main oxidation products. This is crucial in designing reaction systems for the viable production of these value-added chemicals from biomass.

AB - The electrocatalytic oxidation (ECO) of glucose on gold requires alkaline conditions and relatively high potentials (>0.3VRHE). Although the adsorption of hydroxide ions (OHads) is also known to occur under these conditions, the generally accepted proton-coupled electron transfer mechanism for sugar ECO does not explicitly state the role of OHads in the sugar adsorption or oxidation steps. To investigate this, we carried out a combined experimental and density functional theory (DFT) study on the ECO of glucose and xylose over a nanogold catalyst under temperature and pH control. Grandcanonical DFT (GC-DFT) was used to identify the preferred reaction mechanism in which OHads facilitates the thermodynamically feasible formation of gluconic and xylonic acid. Calculated results also showed that OHads plays a role in improving the acid selectivity. Constant-potential electrolyses in sugar solutions were performed using mesoporous (Sibunit) carbon-supported Au nanoparticles (AuNPs) with an average cluster size of 4.7nm. Experimental results showed that the highest conversions for glucose (57.7%) and xylose (49.4%) were obtained at 25°C and pH12.5, with gluconic and xylonic acid selectivity of 81.5 and 87.8 %, respectively. The catalytic activities were high considering the low Au loading (∼0.1%wt). Higher pH led to a decrease in the ECO rate possibly due to excess hydroxide ions blocking active sites for sugar adsorption. Our results highlight the importance of computational studies in elucidating reaction mechanisms for sugar ECO where sugar acids are the main oxidation products. This is crucial in designing reaction systems for the viable production of these value-added chemicals from biomass.

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