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Engineering acid site spatial location of zeolite catalyst harbors tremendous potential to boost catalytic performance but still remains a grand challenge for aromatization reaction. Herein, we successfully manipulate acid site spatial location inside the ZSM‐5 channels to promote the hexane aromatization via the simple SiO2 coating treatment. Multi‐techniques demonstrated that the medium strong L acid in the channel originated from the Si(Al)OZn structure is mainly retained in the Zn/ZSM‐5‐Si catalyst by covering the acid sites outside the channel. Surprisingly, there is a good linear relationship between BTEX yield and this medium strong L acid content. Based on the reaction kinetics, in situ FT‐IR and theoretical calculations, it is found that the L acid with confinement effect served as the main active site could prominently enhance the cyclization of propene intermediate and the dehydrogenation of cycloalkane due to the strong affinity between the C/H and ZnOx, and control the desorption of BTEX (mainly benzene, toluene, ethylbenzene, and p‐xylene) by weakening the binding of hydrogen proton to π electrons. Compared with the ordinary Zn/ZSM‐5 catalyst, the yield of BTEX is increased by nearly 10%, and the Zn/ZSM‐5‐Si catalyst exhibits excellent anti coking deactivation ability. This strategy together with mechanistic results may pave the rational design of efficient Zn/ZSM‐5 catalysts for aromatization reaction. [ABSTRACT FROM AUTHOR]

We successfully realized the highly selective aromatization of n-hexane by the assistance of CO 2 over Zn modified HZSM-5 catalyst. The in situ H originated from the C-H activation of n-hexane and cyclohexane could be timely removed through the dynamic evolution between CO 2 and Lewis acid site, thus inhibiting the hydrogen transfer side reaction and promoting the desorption of BTEX. Therefore, the Zn/ZSM-5-CO 2 catalyst exhibits as high as 49.7% BTEX yield, which is nearly 10% higher than that of the Zn/ZSM-5-N 2 catalyst (40.3%). [Display omitted] • The introduction of CO 2 could timely remove the in situ H. • Hydrogen transfer between olefins and aromatics is effectively inhibited. • The binding of hydrogen proton to π electrons is weakened. • The loss of medium strength Lewis acid is significantly reduced. • The Zn/ZSM-5-CO 2 catalyst exhibits as high as 49.7% BTEX yield and superior catalytic stability. Controlling the evolution of H species in CO 2 -assisted alkane activation represents an opportunity for simultaneously upgrading light alkanes and greenhouse gas CO 2. Herein, we successfully realized the highly selective aromatization of n -hexane by the assistance of CO 2 over Zn modified HZSM-5 catalyst. Multi-characterizations demonstrated that the introduction of CO 2 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-CO 2 displays a record high 49.7% BTEX yield, which is nearly 10% higher than that of the Zn/ZSM-5-N 2 (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. [ABSTRACT FROM AUTHOR]