Oxidative upgrade of furfural to succinic acid using SO3H-carbocatalysts with nitrogen functionalities based on polybenzoxazine

Uthen Thubsuang; Suphawadee Chotirut; Kamchai Nuithitikul; Apirak Payaka; Nicharat Manmuanpom; Thanyalak Chaisuwan; Sujitra Wongkasemjit

doi:10.1016/j.jcis.2020.01.001

Oxidative upgrade of furfural to succinic acid using SO₃H-carbocatalysts with nitrogen functionalities based on polybenzoxazine

J Colloid Interface Sci. 2020 Apr 1:565:96-109. doi: 10.1016/j.jcis.2020.01.001. Epub 2020 Jan 3.

Authors

Uthen Thubsuang¹, Suphawadee Chotirut², Kamchai Nuithitikul², Apirak Payaka³, Nicharat Manmuanpom⁴, Thanyalak Chaisuwan⁴, Sujitra Wongkasemjit⁴

Affiliations

¹ School of Engineering and Technology, Walailak University, Nakhon Si Thammarat 80160, Thailand. Electronic address: uthen.th@wu.ac.th.
² School of Engineering and Technology, Walailak University, Nakhon Si Thammarat 80160, Thailand.
³ School of Science, Walailak University, Nakhon Si Thammarat 80160, Thailand; Research Group in Applied, Computational and Theoretical Science (ACTS), Walailak University, Nakhon Si Thammarat 80160, Thailand.
⁴ The Petroleum and Petrochemical College, Chulalongkorn University, Bangkok 10330, Thailand; Center of Excellence on Petrochemical and Materials Technology, Bangkok 10330, Thailand.

PMID: 31935589
DOI: 10.1016/j.jcis.2020.01.001

Abstract

SO₃H-carbocatalysts with nitrogen functionalities were prepared using the carbonization of polybenzoxazine derived from four different amines (aniline, ethylenediamine, triethylenetetramine, and tetraethylenepentamine) and then sulfonation. The obtained SO₃H-carbocatalysts underwent catalytic testing for furfural oxidation with H₂O₂ to produce succinic acid. The effects of nitrogen functionalities were reported for the first time. The results showed that all carbon samples exhibited a microporous characteristic with comparable textural properties and contained various nitrogen functionalities (N-6, N-5, N-Q, and N-X). After sulfonation, the SO₃H-carbocatalyst prepared from tetraethylenepentamine-based polybenzoxazine had the highest amount of sulfonic acid groups (1.45 mmol g^-1) and a high nitrogen content (4.23%), providing a maximum succinic acid yield of 93.0% within a rapid reaction time of 60 min under the optimized conditions. This was higher than from Amberlyst-type catalysts and SO₃H-carbocatalyst without nitrogen functionalities and was ascribed to the synergistic activity of the sulfonic acid groups and nitrogen functionalities. The XPS spectra and computational study confirmed that such nitrogen functionalities, especially N-5, are capable of forming hydrogen bonding with furfural, facilitating the formation of an intermediate compound and thereby enhancing the catalytic efficiency. However, after four cycles, the succinic acid yield decreased to 40% due to leaching of the sulfonic acid groups.

Keywords: Carbocatalyst; Furfural; Polybenzoxazine; Pore; Porous carbon; Succinic acid.