Surface‐Engineered Clay Nanoreactors for Boosting Suzuki‐Miyaura Coupling Under 2D Confinement

ABSTRACT

Studies related to the influence of molecular confinement on chemical reactivity are essential for both understanding biological systems and advanced catalytic processes. In this work, we report the design and fabrication of surface‐tunable two‐dimensional (2D) nanoreactors (NR) constructed through layer‐by‐layer assembly of exfoliated vermiculite (VM) and picolinate‐functionalized vermiculite ( VM _pico ) sheets decorated with Pd nanoparticles. The resulting nanoreactors, VM‐Pd‐NR and VM _pico ‐Pd‐NR, produce confined nanofluidic environments that significantly enhance the catalytic performance of the Suzuki–Miyaura coupling (SMC) reaction, a widely used method for carbon–carbon (C‐C) bond formation. The 2D nanoreactors accelerate the reaction rate by more than 9000‐fold compared with conventional heterogeneous stirring. Notably, the VM _pico ‐Pd‐NR demonstrates an exceptional turnover frequency (TOF) of 317,683 h ^{− 1} , among the highest reported for this transformation. The VM _pico ‐Pd‐NR enables complete conversion (∼100%) of iodobenzene to biphenyl within 5.9 s at room temperature, in contrast to only 37% (60 s) of conversion achieved through traditional stirring. Increasing local reactant concentrations and altering vibrational energy distributions due to synergy of confinement and molecules are attributed to the lowering of the activation barrier and accelerating the reaction by ∼10 ⁴ times. Furthermore, a range of arylboronic acids exhibit similarly boosted conversion rates within the nanoreactors.