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ORIGINAL RESEARCH article
Front. Chem.
Sec. Green and Sustainable Chemistry
Volume 13 - 2025 | doi: 10.3389/fchem.2025.1588773
This article is part of the Research Topic Renewable Chemistry View all 6 articles
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With the growing global concern over CO₂ emissions, reducing CO₂ output has become an urgent requirement. Ironmaking is among the highest CO₂-emitting industries, primarily due to the use of coke as a reductant and the use of a heat source at around 2,000 °C. To address this issue, various alternative reductants, including CO, H₂, and lignite, have been explored. Building on these efforts, we recently reported a novel ironmaking system utilizing oxalic acid (HOOC-COOH) as the reductant. Formate salts, hydrogenated forms of CO₂, are promising precursors for oxalate salts; however, their behavior during dimerization remains poorly understood. Herein, we investigate the influence of group 1 and 2 metal cations on the base-promoted dehydrogenative coupling of formate to form oxalate. Treatment of sodium formate with various bases (group 1 and 2 metal carbonates or hydroxides) revealed that group 1 metal hydroxides are more effective than metal carbonates for oxalate formation, with cesium hydroxide (CsOH) exhibiting high reactivity. Density functional theory (DFT) calculations suggest that this kinetic advantage arises not only from increased basicity but also from intermediate destabilization in the Na/Cs mixed cation system. Additionally, both experimental and theoretical investigations reveal that oxalate yield is influenced by the thermodynamic stability of intermediates and products (oxalate salts), highlighting the crucial role of cations in the reaction.
Keywords: Formate anion, Oxalate dianion, CO2, Alkali metal cations, DFT calculation
Received: 06 Mar 2025; Accepted: 25 Mar 2025.
Copyright: © 2025 Tahara, Mori, Hayashi and Kudo. This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) or licensor are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.
* Correspondence:
Atsushi Tahara, Tohoku University, Sendai, Japan
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