Encapsulating Metal Nanoparticles into a Layered Zeolite Precursor with Surface Silanol Nests Enhances Sintering Resistance**

Abstract Supported metal nanoparticles are used as heterogeneous catalysts but often deactivated due to sintering at high temperatures. Confining metal species into a porous matrix reduces sintering, yet supports rarely provide additional stabilization. Here, we used the silanol‐rich layered zeolite IPC‐1P to stabilize ultra‐small Rh nanoparticles. By adjusting the IPC‐1P interlayer space through swelling, we prepared various architectures, including microporous and disordered mesoporous. In situ scanning transmission electron microscopy confirmed that Rh nanoparticles are resistant to sintering at high temperature (750 °C, 6 hrs). Rh clusters strongly bind to surface silanol quadruplets at IPC‐1P layers by hydrogen transfer to clusters, while high silanol density hinders their migration based on density functional theory calculations. Ultimately, combining swelling with long‐chain surfactant and utilizing metal‐silanol interactions resulted in a novel, catalytically active material—Rh@IPC_C22.