In Situ Sulfide-Induced Surface Reconstruction of Catalysts for Enhanced Hydrogenation Efficiency and Sulfur Resistance
Bingcheng Li, Wei He, Jie Liu, Xinhui Zhang, Rubo Fang, Xiao Zhang, Zhongliang Shi, Chunshan Lu, Feng Feng, Qunfeng Zhang, Qingtao Wang, Xiao‐Nian Li
Abstract
The development of sulfur-resistant nonhomogeneous noble metal catalysts with high activity and stability remains a significant challenge. In this work, Pd 4 S/ZSM-5 catalysts were prepared via in situ sulfidation-induced catalyst surface reconstruction and their sulfur-resistant performance in the hydrogenation of sulfur-containing substrates was systematically evaluated. Structural analysis revealed that Pd/ZSM-5 and Pd 4 S/ZSM-5 catalysts had similar morphologies and physicochemical properties. However, they differed notably in hydrogenation activity (Pd > Pd 4 S) and sulfur resistance (Pd < Pd 4 S). Overall, Pd 4 S/ZSM-5 has the best stability for catalytic hydrogenation of sulfur-containing substrates in sulfur-containing systems, and its turnover frequency (1471 h –1 ) is about 5 times higher than that of Pd x S y /C (281.09 h –1 ) during the hydrogenation of 4-nitrothioanisole. Furthermore, Pd 4 S/ZSM-5 retained its activity across at least 10 reactions without significant deactivation. System characterization and density functional theory calculations suggest that the enhanced sulfur resistance of Pd 4 S/ZSM-5 is due to the reduced adsorption strength and energy of the sulfur-containing molecules, along with the improved selectivity for –NO 2 . This study provides valuable insights for designing and optimizing sulfur-resistant noble metal catalysts.