The powerful combination of 2D/2D Ni-MOF/carbon nitride for deep desulfurization of thiophene in fuel: Conversion route, DFT calculation, mechanism

Xiaoyu Zhou; Lei Zhang; Hang Liu; Qing Yang; Shan Zhu; Haonan Wu; Teruhisa Ohno; Yu Zhang; Tianyi Wang; Dawei Su; Chengyin Wang

doi:10.1016/j.jcis.2023.12.105

The powerful combination of 2D/2D Ni-MOF/carbon nitride for deep desulfurization of thiophene in fuel: Conversion route, DFT calculation, mechanism

J Colloid Interface Sci. 2024 Mar 15:658:627-638. doi: 10.1016/j.jcis.2023.12.105. Epub 2023 Dec 18.

Authors

Xiaoyu Zhou¹, Lei Zhang¹, Hang Liu¹, Qing Yang¹, Shan Zhu¹, Haonan Wu¹, Teruhisa Ohno², Yu Zhang³, Tianyi Wang⁴, Dawei Su⁵, Chengyin Wang⁶

Affiliations

¹ College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, China.
² Department of Applied Chemistry, Faculty of Engineering, Kyushu Institute of Technology, Kitakyushu 804-8550, Japan.
³ School of Nursing, Yangzhou University, 136 Jiangyang Middle Road, Yangzhou 225009, China.
⁴ College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, China. Electronic address: wangty@yzu.edu.cn.
⁵ School of Mathematical and Physical Sciences, Faculty of Science, University of Technology Sydney, Sydney, NSW 2007, Australia. Electronic address: dawei.su@uts.edu.au.
⁶ College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, China. Electronic address: wangcy@yzu.edu.cn.

PMID: 38134671
DOI: 10.1016/j.jcis.2023.12.105

Abstract

2D/2D Ni-MOF/g-C₃N₄ nanocomposite was utilized for desulfurization. The multilayer pore structure and high specific surface area of Ni-MOF/g-C₃N₄ promote the adsorption and conversion of thiophene. In addition, the two-dimensional structure exposes more active centers and shortens photogenerated carrier migration to the material surface distance, it enhances photogenerated charge transfer. The Ni-MOF and g-C₃N₄ construct a Z-scheme heterojunction structure with tight contact, it effectively enhances the material's photocatalytic redox ability. In the light, the material generates more photocarriers for the production of free radicals including hydroxyl radicals, holes, and superoxide radicals. The higher carrier concentration of Ni-MOF/g-C₃N₄ promotes the activation and oxidation of thiophene, consequently enhancing the photocatalytic desulfurization capability. The results showed that the conversion of thiophene was 98.82 % in 3 h under visible light irradiation. Radical capture experiments and analysis using electron paramagnetic resonance spectroscopy demonstrated that superoxide radicals, holes, and hydroxyl radicals played crucial roles in PODS (photocatalytic oxidative desulfurization). In addition, DFT (density functional theory) calculations were conducted to determine the paths of electron migration and TH (thiophene) adsorption energy. Finally, a mechanism for photocatalytic desulfurization was proposed based on the comprehensive analysis of theoretical calculations and experimental studies.

Keywords: 2D/2D; Ni-MOF/g-C(3)N(4); Photocatalytic oxidative desulfurization; Thiophene.