Modulation of Pt states on Pt/ZnO for atmospheric ultra-deep desulfurization of dibenzothiophene and sustainable utilization

Abstract

The relationship between active metals and desulfurization activity, ultra-deep desulfurization at atmospheric pressure, and the sustainable utilization of ZnO-based adsorbents are positive significance for designing high-efficiency adsorbents in the field of reactive adsorption desulfurization (RADS) to achieve atmospheric zero sulfur and promote sustainable development of adsorbents. However, no efficient approach has been developed to systematically and simultaneously study all three aspects. In this work, we explored Pt/ZnO with different Pt states by metal-support interaction and oxygen vacancy modulation for atmospheric RADS of dibenzothiophene (DBT). The relationship between metal-active Pt states and the desulfurization activity of DBT was well established. The limiting step of atmospheric DBT desulfurization over Pt/ZnO was proposed, providing a new understanding and supplementing of the current RADS reaction. Moreover, the feasibility of Pt/ZnO to achieve ultra-deep desulfurization of DBT under atmospheric H2 pressure was analyzed from kinetics (51.8 kJ/mol) and thermodynamics (kRADS = 4.4*10^7). The spent Pt/ZnO adsorbent with a saturated sulfur capacity could be sustainable utilized as a highly efficient (408 μmolDBT/gPt*min) and sulfur-tolerant (155 h) catalyst for DBT hydrodesulfurization. The work aims to suggest designs for efficient and sustainable adsorbents based on Pt/ZnO for ultra-deep desulfurization at atmospheric pressure, establishing the scientific basis for industrial applications of this process.