Jiang Nan, Zhou Xiao, Jiang Yi-Fan, Zhao Zhi-Wei, Ma Liu-Bo, Shen Cong-Cong, Liu Ya-Nan, Yuan Cheng-Zong, Sahar Shafaq, Xu An-Wu
Division of Nanomaterials and Chemistry, Hefei National Laboratory for Physical Sciences at Microscale, University of Science and Technology of China Hefei Anhui 230026 People's Republic of China
RSC Adv. 2018 May 14;8(31):17504-17510. doi: 10.1039/c8ra02831a. eCollection 2018 May 9.
The design and development of highly efficient and long lifetime Pd-based catalysts for hydrogenation reactions have attracted significant research interest over the past few decades. Rational selection of supports for Pd loadings with strong metal-support interaction (SMSI) is beneficial for boosting catalytic activity and stability. In this context, we have developed a facile approach for uniformly immobilizing ultra-small Pd nanoparticles (NPs) with a clean surface on a PrO support by a hydrogen thermal reduction method. The hydrogenations of -nitrophenol and styrene are used as model reactions to evaluate the catalytic efficiency. The results show highly efficient styrene hydrogenation performance under 1 atm H at room temperature with a TOF value as high as 8957.7 h, and the rate constant value of -nitrophenol reduction is 0.0191 s. Strong metal-support interaction and good dispersion of Pd nanoparticles, as demonstrated by XPS and HRTEM results, contribute to the excellent hydrogenation performance. Electron paramagnetic resonance (EPR) results suggest the presence of oxygen vacancies in the support, which serve as electron donors and enhance the adsorption and activation of reactants and subsequent conversion into products. Moreover, the catalyst can be recovered and reused up to 10 consecutive cycles without marked loss of activity. Overall, our results indicate that oxygen-deficient PrO nanorods (NRs) not only play a role as support but also work as the promoter to substantially boost the catalytic activities for organic transformations, therefore, providing a novel strategy to develop other high-performance nanostructured catalysts for environmental sustainability.
在过去几十年中,用于氢化反应的高效且长寿命钯基催化剂的设计与开发引起了广泛的研究兴趣。合理选择具有强金属-载体相互作用(SMSI)的钯负载载体有利于提高催化活性和稳定性。在此背景下,我们开发了一种简便的方法,通过氢热还原法将表面洁净的超小钯纳米颗粒(NPs)均匀固定在PrO载体上。以对硝基苯酚和苯乙烯的氢化反应作为模型反应来评估催化效率。结果表明,在室温1个大气压氢气条件下,苯乙烯氢化反应具有高效性能,TOF值高达8957.7 h⁻¹,对硝基苯酚还原反应的速率常数为0.0191 s⁻¹。XPS和HRTEM结果表明,强金属-载体相互作用以及钯纳米颗粒的良好分散性有助于优异的氢化性能。电子顺磁共振(EPR)结果表明载体中存在氧空位,这些氧空位作为电子供体,增强了反应物的吸附和活化以及随后向产物的转化。此外,该催化剂可以回收并重复使用多达10个连续循环而活性无明显损失。总体而言,我们的结果表明,缺氧的PrO纳米棒(NRs)不仅作为载体发挥作用,还作为促进剂大幅提高有机转化的催化活性,因此,为开发其他用于环境可持续性的高性能纳米结构催化剂提供了一种新策略。