Controlling the evolution of H species in CO₂-assisted alkane activation represents an opportunity for simultaneously upgrading light alkanes and greenhouse gas CO₂. Herein, we successfully realized the highly selective aromatization of n-hexane by the assistance of CO₂ over Zn modified HZSM-5 catalyst. Multi-characterizations demonstrated that the introduction of CO₂ could timely remove the in situ H originated from the C-H activation of n-hexane and cyclohexane through the dynamic evolution of the pentagonal coordination Zn-OH⁺-(CO)-O-Zn structure. On this basis, hydrogen transfer between olefins and aromatics is effectively inhibited, and the binding between π electrons of benzene ring and hydrogen proton is weakened, accelerating the generation and desorption of BTEX. Therefore, the Zn/ZSM-5-CO₂ displays a record high 49.7% BTEX yield, which is nearly 10% higher than that of the Zn/ZSM-5-N₂ (40.3%). In addition, the loss of medium strength Lewis acid caused by in situ H reduction of Si(Al)-O-Zn structure is significantly reduced, ensuring its superior catalytic stability under long-term conditions. These results may provide some insights for the profitable utilization of petrochemical resources to aromatics over zeolites.

_{控制 CO 2}辅助烷烃活化中 H 物种的演化代表了同时升级轻质烷烃和温室气体 CO ₂的机会。在此，我们在Zn改性的HZSM-5催化剂上成功地实现了CO ₂辅助下正己烷的高选择性芳构化。多重表征表明，CO ₂的引入可以通过五角配位Zn-OH ⁺的动态演化及时去除正己烷和环己烷CH活化产生的原位H-(CO)-O-Zn结构。在此基础上有效抑制了烯烃与芳烃之间的氢转移，削弱了苯环π电子与氢质子的结合，加速了苯系物的生成和解吸。因此，Zn/ZSM-5-CO ₂显示出创纪录的 49.7% BTEX 产率，比 Zn/ZSM-5-N ₂ (40.3%) 高出近 10%。此外， Si(Al)-O-Zn结构原位H还原引起的中等强度路易斯酸损失显着减少，确保了其在长期条件下优异的催化稳定性。这些结果可能为将石化资源用于芳烃而非沸石的盈利利用提供一些见解。