Synergetic Effect of Ultrasmall Metal Clusters and Zeolites Promoting Hydrogen Generation

Taking advantage of the synergetic effect of confined ultrasmall metal clusters and zeolite frameworks is an efficient strategy for improving the catalytic performance of metal nanocatalysts. Herein, it is demonstrated that the synergetic effect of ultrasmall ruthenium (Ru) clusters and intrinsic Br？nsted acidity of zeolite frameworks can significantly promote the hydrogen generation of ammonia borane (AB) hydrolysis. Ultrasmall Ru clusters are embedded onto the silicoaluminophosphate SAPO‐34 (CHA) and various aluminosilicate zeolites (MFI, *BEA, and FAU) with tunable acidities by a facile incipient wetness impregnation method. Evidenced by high‐resolution scanning transmission electron microscopy, the sub‐nanometric Ru clusters are uniformly distributed throughout the zeolite crystals. The X‐ray absorption spectroscopy measurements reveal the existence of Ru‐H species between Ru clusters and adjacent Br？nsted acid sites of zeolites, which could synergistically activate AB and water molecules, significantly enhancing the hydrogen evolution rate of AB hydrolysis. Notably, the Ru/SAPO‐34‐0.8Si (Si/Al = 0.8) and Ru/FAU (Si/Al = 30) catalysts with strong acidities afford high turnover frequency values up to 490 and 627 min？1, respectively. These values are more than a 13‐fold enhancement than that of the commercial Ru/C catalyst, and among the top level over other heterogeneous catalysts tested under similar conditions