Boosting NO Oxidation in the Catalytic Peroxone Process over TiO(2): The Key Role of Surface Sulfate

在TiO₂催化过氧酮工艺中增强NO氧化:表面硫酸盐的关键作用

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Abstract

Developing facile TiO(2) preparation methods is crucial for advancing the industrial implementation of a catalytic peroxone process for NO oxidation. In this study, three types of precursors, including titanium butoxide (Ti-BO), metatitanic acid (Ti-MTA), and titanyl sulfate (Ti-TOS), were used to synthesize TiO(2). Remarkably, Ti-TOS and Ti-MTA exhibited enhanced activity compared to that of Ti-BO, with 93 and 87% NO oxidation efficiency (373 K, O(3)/NO = 0.4, H(2)O(2)/NO = 1.2, GHSV = 1.2 × 10(5) h(-1)), which is higher than that of Ti-BO (78%). Further investigations revealed that residual sulfate groups (SO(4) (2-)) from precursors enhance Lewis acidity by withdrawing electrons from the Ti(4+) sites, thereby facilitating H(2)O(2) deprotonation and Ti-OOH formation. This accelerates radical generation for NO oxidation while inhibiting nitrate accumulation and weakening NO adsorption to optimize reaction kinetics. In addition, sulfates also inhibit the accumulation of oxidation product nitrates on the catalyst surface, thereby improving catalytic stability. This work reveals the promotion mechanism of SO(4) (2-) on the catalytic peroxone process from multiple perspectives.

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