Confinement of CsPbBr₃ Perovskite Nanocrystals into Extra-large-pore Zeolite for Efficient and Stable Photocatalytic Hydrogen Evolution

Metal halide perovskites (MHPs), renowned for their outstanding optoelectronic properties, hold significant promise as photocatalysts for hydrogen evolution reaction (HER). However, the low stability and insufficient exposure of catalytically active sites of bulky MHPs seriously impair their catalytic efficiency. Herein, we utilized an extra-large-pore zeolite ZEO-1 (JZO) as a host to confine and stabilize the CsPbBr₃ nanocrystals (3.4 nm) for boosting hydrogen iodide (HI) splitting. The as-prepared CsPbBr₃@ZEO-1 featured sufficiently exposed active sites, superior stability in acidic media, along with intrinsic extra-large pores of ZEO-1 that were favorable for molecule/ion adsorption and diffusion. Most importantly, the unique nanoconfinement effect of ZEO-1 led to the narrowing of the band gap of CsPbBr₃, allowing for more efficient light utilization. As a result, the photocatalytic HER rate of the as-prepared CsPbBr₃@ZEO-1 photocatalyst was increased to 1734 μmol ⋅ h^-1 ⋅ g^-1 _(CsPbBr3) under visible light irradiation compared with bulk CsPbBr₃ (11 μmol ⋅ h^-1 ⋅ g^-1 _(CsPbBr3)), and the long-term durability (36 h) can be achieved. Furthermore, Pt was incorporated with well-dispersed CsPbBr₃ nanocrystals into ZEO-1, resulting in a significant enhancement in activity (4826 μmol ⋅ h^-1 ⋅ g^-1 _(CsPbBr3)), surpassing most of the Pt-integrated perovskite-based photocatalysts. Density functional theory (DFT) calculations and charge-carrier dynamics investigation revealed that the dramatically boosted photocatalytic performance of Pt/CsPbBr₃@ZEO-1 could be attributed to the promotion of charge separation and transfer, as well as to the substantially lowered energy barrier for HER. This work highlights the advantage of extra-large-pore zeolites as the nanoscale platform to accommodate multiple photoactive components, opening up promising prospects in the design and exploitation of novel zeolite-confined photocatalysts for energy harvesting and storage.