The silanization is an important approach for hierarchical zeolite preparation. Although the influences of the silanization conditions have been detailed studied, the differences in the reactivity of the zeolite precursor should further be analyzed. In this paper, hierarchical titanium silicalite-1 (HTS) was prepared with trimethoxy[3-(phenylamino)propyl]silane (TMPAPS) under the n_TMPAPS:n_Si = 0.04–0.20 and n_Ti:n_Si = 0.005–0.04 conditions, the changes of the corresponding physicochemical properties were analyzed, and the influences of the condensation activities between silicon/titanium to the organosialne were deduced and verified by density functional theory (DFT) calculations. Generally, more supermicropores and mesopores can be created in the metastable sponge-like HTS crystals with higher TMPAPS and titanium contents. In comparison, the free energy barrier in the condensation reaction with titanium (1.31 eV) is lower than silicon (1.55 eV), it's preferential to prepare HTS with more intracrystalline secondary porosity by increasing the n_Ti:n_Si. More importantly, the titanium can be isolated by the organosilane, and HTS with more framework titanium can be synthesized by silanization.

硅烷化是分级沸石制备的重要途径。尽管已经详细研究了硅烷化条件的影响，但应进一步分析沸石前体反应性的差异。在本文中，在n _TMPAPS : n _Si  = 0.04-0.20 和n _Ti : n _Si = 0.005-0.04条件下，分析了相应理化性质的变化，并通过密度泛函理论（DFT）计算推导出并验证了硅/钛之间的缩合活性对有机硅烷的影响。通常，在具有较高 TMPAPS 和钛含量的亚稳态海绵状 HTS 晶体中可以产生更多的超微孔和中孔。相比之下，与钛的缩合反应的自由能垒（1.31 eV）低于硅（1.55 eV），通过增加n _Ti : n _Si优先制备具有更多晶内二次孔隙率的 HTS. 更重要的是，有机硅烷可以分离出钛，硅烷化可以合成具有更多骨架钛的HTS。