In-Situ Investigations of Polyoxometalate-Catalysed Biomass Oxidation to Formic Acid by Using Multinuclear High Resolution Flow NMR Spectroscopy

Jan Dominik H. Krueger; Maximilian J. Poller; Catherine Lyall; John Lowe; Ulrich Hintermair; Jakob Albert

doi:10.1002/cctc.202400402

In-Situ Investigations of Polyoxometalate-Catalysed Biomass Oxidation to Formic Acid by Using Multinuclear High Resolution Flow NMR Spectroscopy

Jan Dominik H. Krueger, Maximilian J. Poller, Catherine Lyall, John Lowe, Ulrich Hintermair, Jakob Albert

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

2 Citations (SciVal)

Abstract

Biomass valorisation over polyoxometalate-based (POM) catalysts is a promising strategy for green and sustainable chemistry. In order to further improve such processes e. g. by using different additives, a better understanding of the chemical influence of various additives on the catalyst is paramount. The main objective of this study is to gain a deeper understanding of the effects caused by various additives on the catalytically active vanadium species in the selective aerobic oxidation of carbohydrates to formic acid (esters). After carefully choosing a suitable model system, the oxidation of glycolaldehyde using the heteropolyacid H₅PV₂Mo₁₀O₄₀ (HPA-2) as a catalyst was studied in situ by Flow Nuclear magnetic resonance (FlowNMR) spectroscopy. These measurements allowed to identify the catalytically active isomer of the HPA-2-catalyst and to observe the influence of additives on the reaction kinetics in situ. These findings provide a good basis for further improving POM-based catalytic aerobic oxidation of biomass.

Original language	English
Article number	e202400402
Journal	ChemCatChem
Early online date	10 Apr 2024
DOIs	https://doi.org/10.1002/cctc.202400402
Publication status	Published - 10 Apr 2024

Data Availability Statement

Data will be made available on request.

Funding

. The authors thank the Royal Society (UF160458 fellowship to UH) and the EPSRC Dynamic Reaction Monitoring Facility at the University of Bath (EP/P001475/1). Funded by the European Union (ERC, BioValCat, Project 101086573). Views and opinions expressed are however those of the author(s) only and do not necessarily reflect those of the European Union or the European Research Council. Neither the European Union nor the granting authority can be held responsible for them. J.\u2010D. H. Krueger and M. J. Poller thank the International Office of Universit\u00E4t Hamburg for covering their travel expenses to the DReaM facility at the University of Bath. We thank our research interns Thu Hanh Pham and Emma Petersen for their contributions to the experimental work. We also thank the division for NMR spectroscopy and the division for central element analytics of the Department of Chemistry conducting NMR experiments and ICP measurements. Open Access funding enabled and organized by Projekt DEAL

Funders	Funder number
Royal Society	UF160458
Royal Society
Engineering and Physical Sciences Research Council	EP/P001475/1
Engineering and Physical Sciences Research Council

Keywords

Biomass oxidation
FlowNMR spectroscopy
formic acid
in-situ investigations
polyoxometalate

ASJC Scopus subject areas

Catalysis
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "In-Situ Investigations of Polyoxometalate-Catalysed Biomass Oxidation to Formic Acid by Using Multinuclear High Resolution Flow NMR Spectroscopy",

abstract = "Biomass valorisation over polyoxometalate-based (POM) catalysts is a promising strategy for green and sustainable chemistry. In order to further improve such processes e. g. by using different additives, a better understanding of the chemical influence of various additives on the catalyst is paramount. The main objective of this study is to gain a deeper understanding of the effects caused by various additives on the catalytically active vanadium species in the selective aerobic oxidation of carbohydrates to formic acid (esters). After carefully choosing a suitable model system, the oxidation of glycolaldehyde using the heteropolyacid H5PV2Mo10O40 (HPA-2) as a catalyst was studied in situ by Flow Nuclear magnetic resonance (FlowNMR) spectroscopy. These measurements allowed to identify the catalytically active isomer of the HPA-2-catalyst and to observe the influence of additives on the reaction kinetics in situ. These findings provide a good basis for further improving POM-based catalytic aerobic oxidation of biomass.",

keywords = "Biomass oxidation, FlowNMR spectroscopy, formic acid, in-situ investigations, polyoxometalate",

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AU - Poller, Maximilian J.

AU - Lyall, Catherine

AU - Lowe, John

AU - Hintermair, Ulrich

AU - Albert, Jakob

PY - 2024/4/10

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N2 - Biomass valorisation over polyoxometalate-based (POM) catalysts is a promising strategy for green and sustainable chemistry. In order to further improve such processes e. g. by using different additives, a better understanding of the chemical influence of various additives on the catalyst is paramount. The main objective of this study is to gain a deeper understanding of the effects caused by various additives on the catalytically active vanadium species in the selective aerobic oxidation of carbohydrates to formic acid (esters). After carefully choosing a suitable model system, the oxidation of glycolaldehyde using the heteropolyacid H5PV2Mo10O40 (HPA-2) as a catalyst was studied in situ by Flow Nuclear magnetic resonance (FlowNMR) spectroscopy. These measurements allowed to identify the catalytically active isomer of the HPA-2-catalyst and to observe the influence of additives on the reaction kinetics in situ. These findings provide a good basis for further improving POM-based catalytic aerobic oxidation of biomass.

AB - Biomass valorisation over polyoxometalate-based (POM) catalysts is a promising strategy for green and sustainable chemistry. In order to further improve such processes e. g. by using different additives, a better understanding of the chemical influence of various additives on the catalyst is paramount. The main objective of this study is to gain a deeper understanding of the effects caused by various additives on the catalytically active vanadium species in the selective aerobic oxidation of carbohydrates to formic acid (esters). After carefully choosing a suitable model system, the oxidation of glycolaldehyde using the heteropolyacid H5PV2Mo10O40 (HPA-2) as a catalyst was studied in situ by Flow Nuclear magnetic resonance (FlowNMR) spectroscopy. These measurements allowed to identify the catalytically active isomer of the HPA-2-catalyst and to observe the influence of additives on the reaction kinetics in situ. These findings provide a good basis for further improving POM-based catalytic aerobic oxidation of biomass.

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In-Situ Investigations of Polyoxometalate-Catalysed Biomass Oxidation to Formic Acid by Using Multinuclear High Resolution Flow NMR Spectroscopy

Abstract

Data Availability Statement

Funding

Keywords

ASJC Scopus subject areas

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