Di‑tert‑butyl peroxide (DTBP), an important substance in chemical production, is widely used in olefin polymerization and the improving anti-knock performance of diesel. DTBP synthesized from isobutane selective peroxidation can not only improve the utilization of isobutane resources but also overcome the defects in conventional DTBP synthesis methods. In this work, sulfated TiO₂ (STiO₂) was developed to catalyze isobutane selective peroxidation to DTBP for the first time. The results demonstrated that high oxygen conversion (>90 %) and DTBP selectivity (>31 wt%) were obtained under the optimal reaction condition. Furthermore, after excluding the effect of mass transfer by designing the experiment and calculation, it is concluded that the reaction activity is related to the total amount of acid site and oxygen adsorption capacity, and the DTBP selectivity depended on the amount of surface S=O site. With the basis that the adsorption state of the intermediate product (tert‑butyl hydroperoxide) on the surface S=O site is ensured by in-situ FT-IR characterization and DFT calculation, the reaction mechanism is proposed. It is worth noting that the performance of the STiO₂ catalyst is significantly better than our previously reported MoO₃ catalyst. This improvement can be attributed to the lower reaction activation energy and, most importantly, the larger amount of the strong acid site originating from the S=O site. This work provides a class of efficient STiO₂ catalysts for DTBP production and the improvement of isobutane utilization.

过氧化二叔丁基（DTBP）是化工生产中的重要物质，广泛用于烯烃聚合和提高柴油的抗爆性能。异丁烷选择性过氧化合成DTBP不仅可以提高异丁烷资源的利用率，而且克服了常规DTBP合成方法的缺陷。本工作首次开发了硫酸化TiO ₂ （STiO ₂ ）来催化异丁烷选择性过氧化生成DTBP。结果表明，在最佳反应条件下获得了较高的氧转化率（>90%）和DTBP选择性（>31wt%）。此外，通过实验设计和计算排除传质的影响后，得出反应活性与酸位总量和氧吸附能力有关，DTBP选择性取决于表面S=O的量地点。通过原位FT-IR表征和DFT计算，在确定中间产物（叔丁基过氧化氢）在表面S=O位点上的吸附状态的基础上，提出了反应机理。值得注意的是，STiO ₂ 催化剂的性能明显优于我们之前报道的 MoO ₃ 催化剂。这种改进可归因于较低的反应活化能，最重要的是，源自 S=O 位点的强酸位点较多。该工作为DTBP生产和提高异丁烷利用率提供了一类高效的STiO ₂ 催化剂。