Gao Shiqin, Wang Bolun, Chen Feijian, He Guangyuan, Zhang Tianjun, Li Lin, Li Junyan, Zhou Yida, Feng Binyao, Mei Donghai, Yu Jihong
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, 130012, Changchun, China.
International Center of Future Science, Jilin University, 130012, Changchun, China.
Angew Chem Int Ed Engl. 2024 Apr 8;63(15):e202319996. doi: 10.1002/anie.202319996. Epub 2024 Feb 23.
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 CsPbBr nanocrystals (3.4 nm) for boosting hydrogen iodide (HI) splitting. The as-prepared CsPbBr@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 CsPbBr, allowing for more efficient light utilization. As a result, the photocatalytic HER rate of the as-prepared CsPbBr@ZEO-1 photocatalyst was increased to 1734 μmol ⋅ h ⋅ g under visible light irradiation compared with bulk CsPbBr (11 μmol ⋅ h ⋅ g ), and the long-term durability (36 h) can be achieved. Furthermore, Pt was incorporated with well-dispersed CsPbBr nanocrystals into ZEO-1, resulting in a significant enhancement in activity (4826 μmol ⋅ h ⋅ g ), 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/CsPbBr@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.
金属卤化物钙钛矿（MHP）以其出色的光电性能而闻名，作为析氢反应（HER）的光催化剂具有巨大潜力。然而，块状MHP的低稳定性和催化活性位点的暴露不足严重损害了它们的催化效率。在此，我们利用超大孔沸石ZEO-1（JZO）作为主体来限制和稳定CsPbBr纳米晶体（3.4纳米），以促进碘化氢（HI）分解。所制备的CsPbBr@ZEO-1具有充分暴露的活性位点、在酸性介质中的优异稳定性，以及ZEO-1固有的超大孔，有利于分子/离子的吸附和扩散。最重要的是，ZEO-1独特的纳米限域效应导致CsPbBr的带隙变窄，从而实现更高效的光利用。结果，与块状CsPbBr（11微摩尔·小时·克）相比，所制备的CsPbBr@ZEO-1光催化剂在可见光照射下的光催化HER速率提高到了1734微摩尔·小时·克，并且可以实现长期耐久性（36小时）。此外，将Pt与分散良好的CsPbBr纳米晶体结合到ZEO-1中，导致活性显著增强（4826微摩尔·小时·克），超过了大多数基于Pt的钙钛矿光催化剂。密度泛函理论（DFT）计算和电荷载流子动力学研究表明，Pt/CsPbBr@ZEO-1显著提高的光催化性能可归因于电荷分离和转移的促进，以及HER的能量势垒大幅降低。这项工作突出了超大孔沸石作为容纳多种光活性成分的纳米级平台的优势，为设计和开发用于能量收集和存储的新型沸石限域光催化剂开辟了广阔前景。
