Self-Assembly of a Hierarchical Metal-Organic Framework at the Liquid/Liquid Interface via π-π Stacking Manipulations in Organoplatinum(IV) Complexes for Methanol Fuel Cells.

This study focuses on the facile synthesis of the hierarchical architecture of zeolitic imidazolate framework-8 (ZIF-8) films containing an ultrasmall amount of Pt(0) by investigating the synthesis of different organoplatinum complexes and manipulating the π-π stacking effect in these complexes at the liquid/liquid interface. The organometallic Pt(IV) precursors were complexes with a formula of [PtXMe 2 (R)(bpy)] (bpy = 2,2'-bipyridine; for complex 2 , R = CH 2 CH═CHC 6 H 5 and X = Br; for complex 3 , R = CH 2 CH═CH 2 and X = Br; for complex 4 , R = Me and X = I) prepared by oxidative addition of cinnamyl bromide, allyl bromide, or methyl iodide to [PtMe 2 (bpy)] (complex 1 ). Different thin films were synthesized starting from three organometallic Pt(IV) precursors (i) by reduction of the Pt complexes at the toluene/water interface ( TF2 - TF4 ), (ii) by encapsulation of the Pt precursors in a ZIF-8 ( TF5 - TF7 ), and (iii) by reduction of the Pt precursors onto a ZIF-8 ( TF8 - TF10 ). The self-assembly of ZIF-8 and different organoplatinum precursors at the interface of two immiscible liquids leads to the preparation of films with well-engineered structures such as rhombic dodecahedra, nanorods, hierarchical architectures, and nanowires, which are very difficult and complicated to synthesize under normal conditions. The ultralow loading of platinum complexes with different degrees of π-π stacking of dangling moieties has a great impact on the structure and morphology (directing agent), which in turn drastically changes the catalytic properties. The obtained films were applied as electrocatalysts for methanol oxidation in fuel cells. The electrocatalytic performance of organoplatinum containing a cinnamyl group in hierarchical architecture TF8 was found to be superior to those of nonhierarchical structures.