Liu Yanan, McCue Alan J, Yang Pengfei, He Yufei, Zheng Lirong, Cao Xingzhong, Man Yi, Feng Junting, Anderson James A, Li Dianqing
State Key Laboratory of Chemical Resource Engineering , Beijing University of Chemical Technology , Beijing , China . Email:
Beijing Engineering Center for Hierarchical Catalysts , Beijing University of Chemical Technology , Beijing 100029 , China.
Chem Sci. 2019 Feb 8;10(12):3556-3566. doi: 10.1039/c8sc05423a. eCollection 2019 Mar 28.
The impregnation method is commonly employed to prepare supported multi-metallic catalysts but it is often difficult to achieve homogeneous and stable alloy structures. In this work, we revealed the dependence of alloying behavior on the support morphology by fabricating Ni-Cu over different shaped CeO. Specifically, nanocube ceria favoured the formation of monometallic Cu and Ni-rich phases whereas polycrystalline and nanorod ceria induced the formation of a mixture of Cu-rich alloys with monometallic Ni. Surprisingly, nanopolyhedron (NP) ceria led to the generation of homogeneous Ni-Cu nanoalloys owing to the equivalent interactions of Ni and Cu species with CeO (111) facets which exposed relatively few coordinative unsaturated sites. More importantly, a strong interfacial effect was observed for Ni-Cu/CeO-NP due to the presence of CeO adjacent to metal sites at the interface, resulting in excellent stability of the alloy structure. With the aid of CeO , NiCu nanoalloys showed outstanding catalytic behaviour in acetylene and hexyne hydrogenation reactions. This study provides valuable insights into how fully alloyed and stable catalysts may be prepared by tailoring the support morphology while still employing a universal impregnation method.
浸渍法通常用于制备负载型多金属催化剂,但往往难以获得均匀且稳定的合金结构。在这项工作中,我们通过在不同形状的CeO上制备Ni-Cu,揭示了合金化行为对载体形态的依赖性。具体而言,纳米立方体氧化铈有利于单金属Cu和富Ni相的形成,而多晶和纳米棒状氧化铈则诱导形成富Cu合金与单金属Ni的混合物。令人惊讶的是,纳米多面体(NP)氧化铈由于Ni和Cu物种与CeO(111)面的等效相互作用,导致生成均匀的Ni-Cu纳米合金,而CeO(111)面暴露的配位不饱和位点相对较少。更重要的是,由于在界面处金属位点附近存在CeO,在Ni-Cu/CeO-NP中观察到强烈的界面效应,从而导致合金结构具有出色的稳定性。借助CeO,NiCu纳米合金在乙炔和己炔加氢反应中表现出优异的催化性能。这项研究为如何在仍然采用通用浸渍法的同时,通过调整载体形态来制备完全合金化且稳定的催化剂提供了有价值的见解。