Department of Chemistry and Shanghai Key Lab of Molecular Catalysis and Innovative Materials, State Key Laboratory of Molecular Engineering of Polymers and Advanced Materials Laboratory, Fudan University , Shanghai 200433, P.R. China.
ACS Nano. 2014 Oct 28;8(10):10455-60. doi: 10.1021/nn503794v. Epub 2014 Sep 29.
Supported metal nanoparticle (NP) catalysts have been widely used in many industry processes and catalytic reactions. Catalyst deactivation is mainly caused by the sintering of supported metal NPs. Hence, understanding the metal NPs' sintering behaviors has great significance in preventing catalyst deactivation. Here we report the metal particle migration inside/between mesochannels by scanning transmission electron microscopy and electron energy loss spectroscopy via an in situ TEM heating technique. A sintering process is proposed that particle migration predominates, driven by the difference of gravitational potential from the height of the uneven internal surface of the mesopores; when the distance of the gold nanoparticles with a size of about 3 and 5 nm becomes short after migration, the coalescence process is completed, which is driven by an "octopus-claw-like" expansion of a conduction electron cloud outside the Au NPs. The supports containing an abundance of micropores help to suppress particle migration and coalescence. Our findings provide the understanding toward the rational design of supported industrial catalysts and other nanocomposites with enhanced activity and stability for applications such as batteries, catalysis, drug delivery, gas sensors, and solar cells.
负载型金属纳米颗粒(NP)催化剂在许多工业过程和催化反应中得到了广泛的应用。催化剂失活主要是由于负载型金属 NPs 的烧结引起的。因此,了解金属 NPs 的烧结行为对于防止催化剂失活具有重要意义。在这里,我们通过原位 TEM 加热技术,利用扫描透射电子显微镜和电子能量损失光谱报告了介孔内/介孔间金属颗粒的迁移。提出了一个烧结过程,颗粒迁移占主导地位,由介孔不均匀内表面高度差引起的重力势能差驱动;当迁移后粒径约为 3nm 和 5nm 的金纳米颗粒之间的距离变短时,在 Au NPs 外的传导电子云的“章鱼爪样”膨胀的作用下,完成了团聚过程。含有丰富微孔的载体有助于抑制颗粒迁移和团聚。我们的发现为负载型工业催化剂和其他纳米复合材料的合理设计提供了深入的理解,这些材料在电池、催化、药物输送、气体传感器和太阳能电池等应用中具有增强的活性和稳定性。