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 Ni1.5Sn 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 Ni1.5Sn 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. Mixed‐metal zeolitic imidazolate frameworks (MM‐ZIFs) were synthesized using a one‐pot method. Subsequent calcination and reduction processes resulted in well‐dispersed Ni−Sn nanoalloy particles (~7 nm) supported on ZnO catalysts. These catalysts exhibited excellent catalytic performance in the glycerol hydrogenolysis reaction, selectively yielding 1,2‐propanediol.