Comparative Study of Si−O−Al and Si−O−Si Bond Stability in HZSM‐5 Zeolite Under Steam and Hot Liquid Water Environments

Abstract Understanding the changes in the zeolite framework and catalytic active sites during zeolite‐based vapor‐phase and aqueous catalytic processes is crucial. Herein, the evolution of framework T atoms (Si and Al) in ammonium hexafluorosilicate (AHFS)‐treated HZSM‐5 zeolite under steam and hot liquid water (HLW) environments was inverstigated using various characterization techniques. In HLW, Si−O−Si bonds exhibit poorer hydrothermal stability than Si−O−Al bonds, in contrast to steam. Significant Si atom leaching occurs regardless of whether the framework tetrahedral Al atoms (Al(IV)‐1) are removed. Similar to steam, Al(IV)‐1 species in HLW sequentially evolve into partially coordinated framework Al species and then into extra‐framework Al (EFAL) species through partial and complete hydrolysis. The generated EFAL species act as Lewis acid sites, but their local structures or chemical environments may differ. These findings reveal the difference in the T−O−T bonds attacked by water molecules: the Si−O−Al bonds are primarily attacked in steam, whereas the Si−O−Si bond are primarily attacked in HLW.