Nickel-Tin Nanoalloy Supported ZnO Catalysts from Mixed-Metal Zeolitic Imidazolate Frameworks for Selective Conversion of Glycerol to 1,2-Propanediol.

The successful synthesis of finely tuned Ni1.5 Sn nanoalloy phases containing ZnO catalyst with a small particle size (6.7 nm) from a mixed-metal zeolitic imidazolate framework (MM-ZIF) is investigated. The catalyst was evaluated for the efficient production of 1,2-propanediol (1,2-PDO) from crude glycerol and comprehensively characterized using several analytical techniques. Among the catalysts, 3Ni1Sn/ZnO (Ni/Sn=3/1) showed the best catalytic performance and produced the highest yield (94.2 %) of 1,2-PDO at ~100 % conversion of glycerol; it also showed low apparent activation energy (15.4 kJ/mol) and excellent stability. The results demonstrated that the synergy between Ni-Sn alloy, finely dispersed Ni metallic sites, and the Lewis acidity of SnOx species-loaded ZnO played a pivotal role in the high activity and selectivity of the catalyst. The confirmation of acetol intermediate and theoretical calculations verify the Ni1.5 Sn phases provide the least energetic pathway for the formation of 1,2-PDO selectively. The reusability of solvent for successive ZIF synthesis, along with the excellent recyclability of the ZIF-derived catalyst, enables an overall sustainable process. We believe that the present synthetic protocol that uses MM-ZIF for the conversion of various biomass-derived platform chemicals into valuable products can be applied to various nanoalloy preparations.

Fabrication of Hierarchical, Porous, Bimetallic, Zeolitic Imidazolate Frameworks with the Incorporation of Square Planar Pd and Its Catalytic Application.

Bimetallic zeolitic imidazolate frameworks (ZIFs) containing two different metal ions can exhibit superior performances when applied in heterogeneous catalysis. Herein, we present a facile one-pot synthesis method for PdCo-ZIFs with various Pd/Co ratios, where Pd(II) ions are successfully incorporated into the Co node sites of the ZIF structure. The local structure of the bimetallic ZIFs was comprehensively investigated by pore-structure, X-ray absorption fine structure, and in situ CO adsorption Fourier transform infrared analyses. The results demonstrated that the framework comprises different coordination geometries of Co (tetrahedral) and Pd (square planar) ions connected by the benzimidazolate ligand. Notably, the inherently nonporous, 2D Co-ZIF structure was transformed into a hierarchical porous structure, and the PdCo-ZIFs exhibited a significantly increased concentration of defects and distorted Co sites. Based on these results, the catalytic performances of the synthesized ZIFs in the cycloaddition of CO2 to epoxides were evaluated under a cocatalyst and solvent-free conditions. The PdCo-ZIFs exhibited significantly higher catalytic activity (maximum turnover frequency, TOF = 2501 h-1) than Co-ZIF (TOF = 65 h-1) and Pd-ZIF (no activity), which revealed that the undercoordinated Co sites with distorted structure are the active sites rather than the incorporated Pd ions. This study provides a facile one-pot method for synthesizing bimetallic ZIFs with mixed-coordination modes, hierarchical porous structures, and modified defect concentrations, which would expand the library of structurally diverse bimetallic ZIFs toward various applications.