State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing 210009, China.
Dalton Trans. 2018 Dec 4;47(47):16862-16875. doi: 10.1039/c8dt03054e.
Nowadays, agglomeration and leaching of metal active sites during reaction and recycle processes are considered to be a thorny problem for noble metal-based catalysts. Therefore, to make improvements, nano-gold was selected as a representative research object for many noble metals. In this study, Au nanoparticles (NPs) and magnetic γ-Fe2O3 were intercalated in situ in the walls of MCM-41 via a one-pot hydrothermal method, in which the intercalation process was preceded by co-condensation of tetraethyl orthosilicate (TEOS) with MPTS-Au complexes ((3-mercaptopropyl)-trimethoxysilane (MPTS), HAuCl4·3H2O), and a Fe3O4 sol. By the confinement of silica, Au NPs and γ-Fe2O3 were well dispersed in the walls of MCM-41, the sintering and loss of Au NPs was highly restricted, and the magnetic property of γ-Fe2O3 facilitated the recycling of Au-based catalysts. Additionally, abundant void defects appeared in MCM-41 by assembly of micelles in different sizes and shapes, greatly improving the surface area of target catalysts (>1800 m2 g-1), which provided more opportunities for contact and collision between reactors and gold active sites, effectively solving the problem of mass transportation. As expected, a series FeAu@MCM-41 catalysts showed superior catalytic activity in the reduction of 4-nitrophenol (4-NP) and organic dyes (MB, RhB, and MO), and these catalysts were recycled five times without significant loss of metal species or catalytic activity. This is attributed to the confinement effect of the silica walls and the excellent magnetic properties of γ-Fe2O3. This special structure of FeAu@MCM-41 catalysts provides more insights for designing and fabricating noble metal-based catalysts with desirable performances.
现如今,在反应和循环过程中金属活性位的团聚和浸出被认为是贵金属基催化剂的一个棘手问题。因此,为了进行改进,选择纳米金作为许多贵金属的代表性研究对象。在这项研究中,通过一锅水热法将金纳米颗粒(NPs)和磁性γ-Fe2O3原位嵌入 MCM-41 的壁中,其中插层过程是通过四乙氧基硅烷(TEOS)与 MPTS-Au 配合物((3-巯丙基)-三甲氧基硅烷(MPTS)、HAuCl4·3H2O)和 Fe3O4 溶胶的共缩合来进行的。通过二氧化硅的限制,Au NPs 和 γ-Fe2O3 在 MCM-41 的壁中得到了很好的分散,Au NPs 的烧结和损失受到了高度的限制,并且 γ-Fe2O3 的磁性有助于 Au 基催化剂的回收。此外,通过不同大小和形状的胶束组装,MCM-41 中出现了丰富的空隙缺陷,大大提高了目标催化剂的比表面积(>1800 m2 g-1),为反应器和金活性位之间的接触和碰撞提供了更多机会,有效地解决了传质问题。不出所料,一系列 FeAu@MCM-41 催化剂在 4-硝基苯酚(4-NP)和有机染料(MB、RhB 和 MO)的还原中表现出优异的催化活性,这些催化剂在不损失金属物种或催化活性的情况下已回收使用了五次。这归因于二氧化硅壁的限制效应和 γ-Fe2O3 的优异磁性。FeAu@MCM-41 催化剂的这种特殊结构为设计和制备具有理想性能的贵金属基催化剂提供了更多的思路。