Stabilization of Extra‐Large‐Pore Zeolite by Boron Substitution for the Production of Commercially Applicable Catalysts

Stable extra‐large‐pore zeolites are desirable for industrial purposes due to their ability to accommodate bulky reactants and diffusion through channels. Although there are several extra‐large pore zeolites reported, stable ones are rare. Thus, their stabilization is a feasible strategy for industrial applications. Here, an extra‐large‐pore zeolite EWT with boron substitution is presented, and the resulting zeolite B‐RZM‐3 increased the thermal stability from 600 °C in its silica form to 850 °C. The crystal structure, determined by combining continuous rotation electron diffraction (cRED) and powder X‐ray diffraction (PXRD), shows that B atoms preferentially substitute the interrupted (HO)T(OT)3 (Q3) sites and are partially converted into 3‐coordination to relax framework deformation upon heating. After Al‐reinsertion post‐treatment, Al‐B‐RZM‐3 shows higher ethylbenzene selectivity and ethylene conversion rate per mol acid site than commercial ZSM‐5 and Beta zeolite in benzene alkylation reaction. Synthesizing extra‐large‐pore zeolite in borosilicate form is a potential approach to stabilize interrupted zeolites for commercial applications. Boron substitution stabilizes the extra‐large‐pore zeolite EWT and increases its thermal stability to 850 °C. B atoms preferentially substitute the interrupted Q3 sites and are partially converted into 3‐coordination to relax framework deformation upon heating. After Al‐reinsertion post‐treatment, it shows higher ethylbenzene selectivity and ethylene conversion rate than commercial ZSM‐5 and Beta zeolite in benzene alkylation reaction.