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Nano Ru-based catalysts, including monometallic Ru and Ru-Zn nanoparticles, were synthesized via a precipitation method. The prepared catalysts were evaluated on partial hydrogenation of benzene towards cyclohexene generation, during which the effect of reaction modifiers, i.e., ZnSO 4 , MnSO 4 , and FeSO 4 , was investigated. The fresh and the spent catalysts were thoroughly characterized by XRD, TEM, SEM, XPS, XRF, and DFT studies. It was found that Zn 2+ or Fe 2+ could be adsorbed on the surface of a monometallic Ru catalyst, where a stabilized complex could be formed between the cations and the cyclohexene. This led to an enhancement of catalytic selectivity towards cyclohexene. Furthermore, electron transfer was observed from Zn 2+ or Fe 2+ to Ru, hindering the catalytic activity towards benzene hydrogenation. In comparison, very few Mn 2+ cations were adsorbed on the Ru surface, for which no cyclohexene could be detected. On the other hand, for Ru-Zn catalyst, Zn existed as rodlike ZnO. The added ZnSO4 and FeSO 4 could react with ZnO to generate (Zn(OH) 2 ) 5 (ZnSO 4 )(H 2 O) and basic Fe sulfate, respectively. This further benefited the adsorption of Zn 2+ or Fe 2+ , leading to the decrease of catalytic activity towards benzene conversion and the increase of selectivity towards cyclohexene synthesis. When 0.57 mol·L -1 of ZnSO 4 was applied, the highest cyclohexene yield of 62.6% was achieved. When MnSO 4 was used as a reaction modifier, H 2 SO 4 could be generated in the slurry via its hydrolysis, which reacted with ZnO to form ZnSO 4 . The selectivity towards cyclohexene formation was then improved by the adsorbed Zn 2+ .

Effect of ZnSO4, MnSO4 and FeSO4 on the Partial Hydrogenation of Benzene over Nano Ru-Based Catalysts