Tian Ge, Chen Guangrui, Yang Guoju, Diao Zhenheng, Bai Risheng, Han Ji, Guan Buyuan, Yu Jihong
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, People's Republic of China.
International Center of Future Science, Jilin University, Changchun 130012, People's Republic of China.
ACS Cent Sci. 2024 May 24;10(8):1473-1480. doi: 10.1021/acscentsci.4c00439. eCollection 2024 Aug 28.
Metal/zeolite hybrid nanoframes featuring highly accessible compartmental environments, abundant heterogeneous interfaces, and diverse chemical compositions are expected to possess significant potential for heterogeneous catalysis, yet their general synthetic methodology has not yet been established. In this study, we developed a two-step -kinetics transformation approach to prepare metal/ZSM-5 hybrid nanoframes with exceptionally open nanostructures, tunable metal compositions, and abundant accessible active sites. Initially, the process involved the formation of single-crystalline ZSM-5 nanoframes through an anisotropic etching and recrystallization kinetic transformation process. Subsequently, through an reaction of the Ni ions and the silica species etched from ZSM-5 nanoframes, layered nickel silicate emerged on both the inner and outer surfaces of the zeolite nanoframes. Upon reduction under a hydrogen atmosphere, well-dispersed Ni nanoparticles were produced and immobilized onto the ZSM-5 nanoframes. Strikingly, this strategy can be extended to immobilize a variety of ultrasmall monometallic and bimetallic alloy nanoparticles on zeolite nanoframes. Benefiting from the structural and compositional advantages, the resultant hybrid nanoframes with a high loading of discrete Ni nanoparticles exhibited enhanced performance in the hydrodeoxygenation of stearic acid into liquid fuels. Overall, the methodology shares fresh insights into the rational construction of intricate frame-like metal/zeolite hybrid nanoreactors for many potential catalytic applications.
具有高度可及的分隔环境、丰富的异质界面和多样化学组成的金属/沸石杂化纳米框架有望在多相催化方面具有巨大潜力，但其通用的合成方法尚未确立。在本研究中，我们开发了一种两步动力学转变方法来制备具有异常开放纳米结构、可调金属组成和大量可及活性位点的金属/ZSM-5杂化纳米框架。首先，该过程涉及通过各向异性蚀刻和重结晶动力学转变过程形成单晶ZSM-5纳米框架。随后，通过镍离子与从ZSM-5纳米框架蚀刻出的硅物种的反应，层状硅酸镍出现在沸石纳米框架的内外表面。在氢气气氛下还原后，产生了分散良好的镍纳米颗粒并固定在ZSM-5纳米框架上。引人注目的是，该策略可扩展到将各种超小单金属和双金属合金纳米颗粒固定在沸石纳米框架上。受益于结构和组成优势，所得具有高负载离散镍纳米颗粒的杂化纳米框架在硬脂酸加氢脱氧转化为液体燃料方面表现出增强的性能。总体而言，该方法为合理构建用于许多潜在催化应用的复杂框架状金属/沸石杂化纳米反应器提供了新的见解。
