Effect of K+ and Ca2+ Cations on Structural Manganese(IV) Oxide for the Aerobic Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid

Thinnaphat Poonsawat; Peerapong Promcharoen; Titiya Meechai; Laksamee Chaicharoenwimolkul Chuaitammakit; Ekasith Somsook

doi:10.1021/acsomega.3c06333

Effect of K⁺ and Ca²⁺ Cations on Structural Manganese(IV) Oxide for the Aerobic Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid

ACS Omega. 2023 Dec 7;8(50):47846-47855. doi: 10.1021/acsomega.3c06333. eCollection 2023 Dec 19.

Authors

Thinnaphat Poonsawat¹, Peerapong Promcharoen¹, Titiya Meechai², Laksamee Chaicharoenwimolkul Chuaitammakit³, Ekasith Somsook¹

Affiliations

¹ NANOCAST Laboratory, Center for Catalysis Science and Technology (CAST), Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Mahidol University, 272 Rama VI Road, Ratchathewi, Bangkok 10400, Thailand.
² Department of Premedical Science, Faculty of Medicine, Bangkokthonburi University, Thawi Watthana, Bangkok 10170, Thailand.
³ Chemistry and Applied Chemistry, Faculty of Science and Technology, Suratthani Rajabhat University, 272 Moo 9, Surat-Nasan Road, Khuntale, Muang, Surat Thani 84100, Thailand.

Abstract

The promising influences of K⁺ and Ca²⁺ ions in the development of effective MnO₂ for the selective oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid (FDCA) were studied for the catalytic performance under a high-pressure reaction of aqueous O₂ (0.5 MPa) in a basic system. Various oxidation states of manganese in MnO₂ were able to accelerate the oxidation of 5-formyl-2-furancarboxylic acid to FDCA in the rate-determining step. The results were in good agreement that Ca²⁺ played a key role in the highest FDCA yield up to 85% due to the associated cations on the local coordination to enhance the high surface area and the electronic effect on the manganese ion. Both K-MnO₂ and Ca-MnO₂ catalysts showed excellent catalytic activities without a significant change in the efficiency in the reusability experiments.